I think the right answer is a combination of Steve Morgan's and Serguei's answers. That's how Internet Explorer does it. The pinvoke call to FindMimeFromData works for only 26 hard-coded mime types. Also, it will give ambigous mime types (such as text/plain or application/octet-stream) even though there may exist a more specific, more appropriate mime type. If it fails to give a good mime type, you can go to the registry for a more specific mime type. The server registry could have more up-to-date mime types.

参考网址:http://msdn.microsoft.com/en-us/library/ms775147(VS.85).aspx

在Urlmon.dll中，有一个名为FindMimeFromData的函数。

来自文档

MIME类型检测或“数据嗅探”是指从二进制数据中确定适当的MIME类型的过程。最终结果取决于服务器提供的MIME类型头、文件扩展名和/或数据本身的组合。通常，只有前256字节的数据是重要的。

因此，从文件中读取第一个(最多)256字节，并将其传递给FindMimeFromData。

@Steve Morgan和@Richard Gourlay，这是一个很好的解决方案，谢谢你们。一个小缺点是，当文件中的字节数为255或以下时，mime类型有时会产生“application/octet-stream”，这对于期望产生“text/plain”的文件来说有点不准确。对于这种情况，我更新了你原来的方法如下:

如果文件中的字节数小于或等于255，并且推导出的mime类型是"application/octet-stream"，那么创建一个新的字节数组，该数组由重复n次的原始文件字节组成，直到字节总数为>= 256。然后重新检查新字节数组上的mime-type。

修改方法:

Imports System.Runtime.InteropServices

<DllImport("urlmon.dll", CharSet:=CharSet.Auto)> _
Private Shared Function FindMimeFromData(pBC As System.UInt32, <MarshalAs(UnmanagedType.LPStr)> pwzUrl As System.String, <MarshalAs(UnmanagedType.LPArray)> pBuffer As Byte(), cbSize As System.UInt32, <MarshalAs(UnmanagedType.LPStr)> pwzMimeProposed As System.String, dwMimeFlags As System.UInt32, _
ByRef ppwzMimeOut As System.UInt32, dwReserverd As System.UInt32) As System.UInt32
End Function
Private Function GetMimeType(ByVal f As FileInfo) As String
    'See http://stackoverflow.com/questions/58510/using-net-how-can-you-find-the-mime-type-of-a-file-based-on-the-file-signature
    Dim returnValue As String = ""
    Dim fileStream As FileStream = Nothing
    Dim fileStreamLength As Long = 0
    Dim fileStreamIsLessThanBByteSize As Boolean = False

    Const byteSize As Integer = 255
    Const bbyteSize As Integer = byteSize + 1

    Const ambiguousMimeType As String = "application/octet-stream"
    Const unknownMimeType As String = "unknown/unknown"

    Dim buffer As Byte() = New Byte(byteSize) {}
    Dim fnGetMimeTypeValue As New Func(Of Byte(), Integer, String)(
        Function(_buffer As Byte(), _bbyteSize As Integer) As String
            Dim _returnValue As String = ""
            Dim mimeType As UInt32 = 0
            FindMimeFromData(0, Nothing, _buffer, _bbyteSize, Nothing, 0, mimeType, 0)
            Dim mimeTypePtr As IntPtr = New IntPtr(mimeType)
            _returnValue = Marshal.PtrToStringUni(mimeTypePtr)
            Marshal.FreeCoTaskMem(mimeTypePtr)
            Return _returnValue
        End Function)

    If (f.Exists()) Then
        Try
            fileStream = New FileStream(f.FullName(), FileMode.Open, FileAccess.Read, FileShare.ReadWrite)
            fileStreamLength = fileStream.Length()

            If (fileStreamLength >= bbyteSize) Then
                fileStream.Read(buffer, 0, bbyteSize)
            Else
                fileStreamIsLessThanBByteSize = True
                fileStream.Read(buffer, 0, CInt(fileStreamLength))
            End If

            returnValue = fnGetMimeTypeValue(buffer, bbyteSize)

            If (returnValue.Equals(ambiguousMimeType, StringComparison.OrdinalIgnoreCase) AndAlso fileStreamIsLessThanBByteSize AndAlso fileStreamLength > 0) Then
                'Duplicate the stream content until the stream length is >= bbyteSize to get a more deterministic mime type analysis.
                Dim currentBuffer As Byte() = buffer.Take(fileStreamLength).ToArray()
                Dim repeatCount As Integer = Math.Floor((bbyteSize / fileStreamLength) + 1)
                Dim bBufferList As List(Of Byte) = New List(Of Byte)
                While (repeatCount > 0)
                    bBufferList.AddRange(currentBuffer)
                    repeatCount -= 1
                End While
                Dim bbuffer As Byte() = bBufferList.Take(bbyteSize).ToArray()
                returnValue = fnGetMimeTypeValue(bbuffer, bbyteSize)
            End If
        Catch ex As Exception
            returnValue = unknownMimeType
        Finally
            If (fileStream IsNot Nothing) Then fileStream.Close()
        End Try
    End If
    Return returnValue
End Function

如果你正在使用。net Framework 4.5或更高版本，现在有一个MimeMapping.GetMimeMapping(filename)方法，它将返回一个字符串，其中包含传递文件名的正确Mime映射。注意，这里使用的是文件扩展名，而不是文件本身中的数据。

文档请见http://msdn.microsoft.com/en-us/library/system.web.mimemapping.getmimemapping

我找到了一个硬编码的解决方案，我希望我能帮助到别人:

public static class MIMEAssistant
{
  private static readonly Dictionary<string, string> MIMETypesDictionary = new Dictionary<string, string>
  {
    {"ai", "application/postscript"},
    {"aif", "audio/x-aiff"},
    {"aifc", "audio/x-aiff"},
    {"aiff", "audio/x-aiff"},
    {"asc", "text/plain"},
    {"atom", "application/atom+xml"},
    {"au", "audio/basic"},
    {"avi", "video/x-msvideo"},
    {"bcpio", "application/x-bcpio"},
    {"bin", "application/octet-stream"},
    {"bmp", "image/bmp"},
    {"cdf", "application/x-netcdf"},
    {"cgm", "image/cgm"},
    {"class", "application/octet-stream"},
    {"cpio", "application/x-cpio"},
    {"cpt", "application/mac-compactpro"},
    {"csh", "application/x-csh"},
    {"css", "text/css"},
    {"dcr", "application/x-director"},
    {"dif", "video/x-dv"},
    {"dir", "application/x-director"},
    {"djv", "image/vnd.djvu"},
    {"djvu", "image/vnd.djvu"},
    {"dll", "application/octet-stream"},
    {"dmg", "application/octet-stream"},
    {"dms", "application/octet-stream"},
    {"doc", "application/msword"},
    {"docx","application/vnd.openxmlformats-officedocument.wordprocessingml.document"},
    {"dotx", "application/vnd.openxmlformats-officedocument.wordprocessingml.template"},
    {"docm","application/vnd.ms-word.document.macroEnabled.12"},
    {"dotm","application/vnd.ms-word.template.macroEnabled.12"},
    {"dtd", "application/xml-dtd"},
    {"dv", "video/x-dv"},
    {"dvi", "application/x-dvi"},
    {"dxr", "application/x-director"},
    {"eps", "application/postscript"},
    {"etx", "text/x-setext"},
    {"exe", "application/octet-stream"},
    {"ez", "application/andrew-inset"},
    {"gif", "image/gif"},
    {"gram", "application/srgs"},
    {"grxml", "application/srgs+xml"},
    {"gtar", "application/x-gtar"},
    {"hdf", "application/x-hdf"},
    {"hqx", "application/mac-binhex40"},
    {"htm", "text/html"},
    {"html", "text/html"},
    {"ice", "x-conference/x-cooltalk"},
    {"ico", "image/x-icon"},
    {"ics", "text/calendar"},
    {"ief", "image/ief"},
    {"ifb", "text/calendar"},
    {"iges", "model/iges"},
    {"igs", "model/iges"},
    {"jnlp", "application/x-java-jnlp-file"},
    {"jp2", "image/jp2"},
    {"jpe", "image/jpeg"},
    {"jpeg", "image/jpeg"},
    {"jpg", "image/jpeg"},
    {"js", "application/x-javascript"},
    {"kar", "audio/midi"},
    {"latex", "application/x-latex"},
    {"lha", "application/octet-stream"},
    {"lzh", "application/octet-stream"},
    {"m3u", "audio/x-mpegurl"},
    {"m4a", "audio/mp4a-latm"},
    {"m4b", "audio/mp4a-latm"},
    {"m4p", "audio/mp4a-latm"},
    {"m4u", "video/vnd.mpegurl"},
    {"m4v", "video/x-m4v"},
    {"mac", "image/x-macpaint"},
    {"man", "application/x-troff-man"},
    {"mathml", "application/mathml+xml"},
    {"me", "application/x-troff-me"},
    {"mesh", "model/mesh"},
    {"mid", "audio/midi"},
    {"midi", "audio/midi"},
    {"mif", "application/vnd.mif"},
    {"mov", "video/quicktime"},
    {"movie", "video/x-sgi-movie"},
    {"mp2", "audio/mpeg"},
    {"mp3", "audio/mpeg"},
    {"mp4", "video/mp4"},
    {"mpe", "video/mpeg"},
    {"mpeg", "video/mpeg"},
    {"mpg", "video/mpeg"},
    {"mpga", "audio/mpeg"},
    {"ms", "application/x-troff-ms"},
    {"msh", "model/mesh"},
    {"mxu", "video/vnd.mpegurl"},
    {"nc", "application/x-netcdf"},
    {"oda", "application/oda"},
    {"ogg", "application/ogg"},
    {"pbm", "image/x-portable-bitmap"},
    {"pct", "image/pict"},
    {"pdb", "chemical/x-pdb"},
    {"pdf", "application/pdf"},
    {"pgm", "image/x-portable-graymap"},
    {"pgn", "application/x-chess-pgn"},
    {"pic", "image/pict"},
    {"pict", "image/pict"},
    {"png", "image/png"}, 
    {"pnm", "image/x-portable-anymap"},
    {"pnt", "image/x-macpaint"},
    {"pntg", "image/x-macpaint"},
    {"ppm", "image/x-portable-pixmap"},
    {"ppt", "application/vnd.ms-powerpoint"},
    {"pptx","application/vnd.openxmlformats-officedocument.presentationml.presentation"},
    {"potx","application/vnd.openxmlformats-officedocument.presentationml.template"},
    {"ppsx","application/vnd.openxmlformats-officedocument.presentationml.slideshow"},
    {"ppam","application/vnd.ms-powerpoint.addin.macroEnabled.12"},
    {"pptm","application/vnd.ms-powerpoint.presentation.macroEnabled.12"},
    {"potm","application/vnd.ms-powerpoint.template.macroEnabled.12"},
    {"ppsm","application/vnd.ms-powerpoint.slideshow.macroEnabled.12"},
    {"ps", "application/postscript"},
    {"qt", "video/quicktime"},
    {"qti", "image/x-quicktime"},
    {"qtif", "image/x-quicktime"},
    {"ra", "audio/x-pn-realaudio"},
    {"ram", "audio/x-pn-realaudio"},
    {"ras", "image/x-cmu-raster"},
    {"rdf", "application/rdf+xml"},
    {"rgb", "image/x-rgb"},
    {"rm", "application/vnd.rn-realmedia"},
    {"roff", "application/x-troff"},
    {"rtf", "text/rtf"},
    {"rtx", "text/richtext"},
    {"sgm", "text/sgml"},
    {"sgml", "text/sgml"},
    {"sh", "application/x-sh"},
    {"shar", "application/x-shar"},
    {"silo", "model/mesh"},
    {"sit", "application/x-stuffit"},
    {"skd", "application/x-koan"},
    {"skm", "application/x-koan"},
    {"skp", "application/x-koan"},
    {"skt", "application/x-koan"},
    {"smi", "application/smil"},
    {"smil", "application/smil"},
    {"snd", "audio/basic"},
    {"so", "application/octet-stream"},
    {"spl", "application/x-futuresplash"},
    {"src", "application/x-wais-source"},
    {"sv4cpio", "application/x-sv4cpio"},
    {"sv4crc", "application/x-sv4crc"},
    {"svg", "image/svg+xml"},
    {"swf", "application/x-shockwave-flash"},
    {"t", "application/x-troff"},
    {"tar", "application/x-tar"},
    {"tcl", "application/x-tcl"},
    {"tex", "application/x-tex"},
    {"texi", "application/x-texinfo"},
    {"texinfo", "application/x-texinfo"},
    {"tif", "image/tiff"},
    {"tiff", "image/tiff"},
    {"tr", "application/x-troff"},
    {"tsv", "text/tab-separated-values"},
    {"txt", "text/plain"},
    {"ustar", "application/x-ustar"},
    {"vcd", "application/x-cdlink"},
    {"vrml", "model/vrml"},
    {"vxml", "application/voicexml+xml"},
    {"wav", "audio/x-wav"},
    {"wbmp", "image/vnd.wap.wbmp"},
    {"wbmxl", "application/vnd.wap.wbxml"},
    {"wml", "text/vnd.wap.wml"},
    {"wmlc", "application/vnd.wap.wmlc"},
    {"wmls", "text/vnd.wap.wmlscript"},
    {"wmlsc", "application/vnd.wap.wmlscriptc"},
    {"wrl", "model/vrml"},
    {"xbm", "image/x-xbitmap"},
    {"xht", "application/xhtml+xml"},
    {"xhtml", "application/xhtml+xml"},
    {"xls", "application/vnd.ms-excel"},                        
    {"xml", "application/xml"},
    {"xpm", "image/x-xpixmap"},
    {"xsl", "application/xml"},
    {"xlsx","application/vnd.openxmlformats-officedocument.spreadsheetml.sheet"},
    {"xltx","application/vnd.openxmlformats-officedocument.spreadsheetml.template"},
    {"xlsm","application/vnd.ms-excel.sheet.macroEnabled.12"},
    {"xltm","application/vnd.ms-excel.template.macroEnabled.12"},
    {"xlam","application/vnd.ms-excel.addin.macroEnabled.12"},
    {"xlsb","application/vnd.ms-excel.sheet.binary.macroEnabled.12"},
    {"xslt", "application/xslt+xml"},
    {"xul", "application/vnd.mozilla.xul+xml"},
    {"xwd", "image/x-xwindowdump"},
    {"xyz", "chemical/x-xyz"},
    {"zip", "application/zip"}
  };

  public static string GetMIMEType(string fileName)
  {
    //get file extension
    string extension = Path.GetExtension(fileName).ToLowerInvariant();

    if (extension.Length > 0 && 
        MIMETypesDictionary.ContainsKey(extension.Remove(0, 1)))
    {
      return MIMETypesDictionary[extension.Remove(0, 1)];
    }
    return "unknown/unknown";
  }
}

最后我确实使用了urlmon.dll。我本以为有更简单的方法，但这招管用。我包含了代码来帮助其他人，并允许我在需要时再次找到它。

using System.Runtime.InteropServices;

...

    [DllImport(@"urlmon.dll", CharSet = CharSet.Auto)]
    private extern static System.UInt32 FindMimeFromData(
        System.UInt32 pBC,
        [MarshalAs(UnmanagedType.LPStr)] System.String pwzUrl,
        [MarshalAs(UnmanagedType.LPArray)] byte[] pBuffer,
        System.UInt32 cbSize,
        [MarshalAs(UnmanagedType.LPStr)] System.String pwzMimeProposed,
        System.UInt32 dwMimeFlags,
        out System.UInt32 ppwzMimeOut,
        System.UInt32 dwReserverd
    );

    public static string getMimeFromFile(string filename)
    {
        if (!File.Exists(filename))
            throw new FileNotFoundException(filename + " not found");

        byte[] buffer = new byte[256];
        using (FileStream fs = new FileStream(filename, FileMode.Open))
        {
            if (fs.Length >= 256)
                fs.Read(buffer, 0, 256);
            else
                fs.Read(buffer, 0, (int)fs.Length);
        }
        try
        {
            System.UInt32 mimetype;
            FindMimeFromData(0, null, buffer, 256, null, 0, out mimetype, 0);
            System.IntPtr mimeTypePtr = new IntPtr(mimetype);
            string mime = Marshal.PtrToStringUni(mimeTypePtr);
            Marshal.FreeCoTaskMem(mimeTypePtr);
            return mime;
        }
        catch (Exception e)
        {
            return "unknown/unknown";
        }
    }