我的问题是在Windows 2003服务器，当调用AuthenticateAsClient。上面的解决方案(例如绕过ServicePointManager.ServerCertificateValidationCallback)不起作用。

原来这是Windows 2003中的一个bug，并且有一个热修复:

"使用加密API的应用程序无法在Windows Server 2003中验证X.509证书"

https://support.microsoft.com/en-us/kb/938397

安装此修复程序解决了我的问题。

我的问题不是通过IP地址而不是URL引用服务器。我从CA处购买了一个签名证书，用于在专用网络中使用。在引用服务器时，证书上指定的URL很重要。当我通过证书中的URL引用服务器时，一切都开始工作了。

还没有人指出明显的，如果你想安全地调试SSL问题，那么总是使用这种方法:

#if DEBUG
    ServicePointManager.ServerCertificateValidationCallback += (sender, cert, chain, sslPolicyErrors) => true;
#endif

即使您不小心提交了代码，它也不会在发布模式下编译。

当我试图通过代理服务器(Usergate)使用SmtpClient发送电子邮件时，我有同样的错误。

验证包含服务器地址的证书，该证书不等于代理服务器地址，因此出现错误。 我的解决方案:当检查证书时发生错误，接收证书，导出并检查。

public static bool RemoteServerCertificateValidationCallback(Object sender, X509Certificate certificate, X509Chain chain, SslPolicyErrors sslPolicyErrors)
    {
        if (sslPolicyErrors == SslPolicyErrors.None)
            return true;

        // if got an cert auth error
        if (sslPolicyErrors != SslPolicyErrors.RemoteCertificateNameMismatch) return false;
        const string sertFileName = "smpthost.cer";

        // check if cert file exists
        if (File.Exists(sertFileName))
        {
            var actualCertificate = X509Certificate.CreateFromCertFile(sertFileName);
            return certificate.Equals(actualCertificate);
        }

        // export and check if cert not exists
        using (var file = File.Create(sertFileName))
        {
            var cert = certificate.Export(X509ContentType.Cert);
            file.Write(cert, 0, cert.Length);
        }
        var createdCertificate = X509Certificate.CreateFromCertFile(sertFileName);
        return certificate.Equals(createdCertificate);
    }

我的电子邮件发件人类的完整代码:

public class EmailSender
{
    private readonly SmtpClient _smtpServer;
    private readonly MailAddress _fromAddress;

    public EmailSender()
    {
        ServicePointManager.ServerCertificateValidationCallback = RemoteServerCertificateValidationCallback;
        _smtpServer = new SmtpClient();
    }

    public EmailSender(string smtpHost, int smtpPort, bool enableSsl, string userName, string password, string fromEmail, string fromName) : this()
    {
        _smtpServer.Host = smtpHost;
        _smtpServer.Port = smtpPort;
        _smtpServer.UseDefaultCredentials = false;
        _smtpServer.EnableSsl = enableSsl;
        _smtpServer.Credentials = new NetworkCredential(userName, password);

        _fromAddress = new MailAddress(fromEmail, fromName);
    }

    public bool Send(string address, string mailSubject, string htmlMessageBody,
        string fileName = null)
    {
        return Send(new List<MailAddress> { new MailAddress(address) }, mailSubject, htmlMessageBody, fileName);
    }

    public bool Send(List<MailAddress> addressList, string mailSubject, string htmlMessageBody,
        string fileName = null)
    {
        var mailMessage = new MailMessage();
        try
        {
            if (_fromAddress != null)
                mailMessage.From = _fromAddress;

            foreach (var addr in addressList)
                mailMessage.To.Add(addr);

            mailMessage.SubjectEncoding = Encoding.UTF8;
            mailMessage.Subject = mailSubject;

            mailMessage.Body = htmlMessageBody;
            mailMessage.BodyEncoding = Encoding.UTF8;
            mailMessage.IsBodyHtml = true;

            if ((fileName != null) && (System.IO.File.Exists(fileName)))
            {
                var attach = new Attachment(fileName, MediaTypeNames.Application.Octet);
                attach.ContentDisposition.CreationDate = System.IO.File.GetCreationTime(fileName);
                attach.ContentDisposition.ModificationDate = System.IO.File.GetLastWriteTime(fileName);
                attach.ContentDisposition.ReadDate = System.IO.File.GetLastAccessTime(fileName);
                mailMessage.Attachments.Add(attach);
            }
            _smtpServer.Send(mailMessage);
        }
        catch (Exception e)
        {
            // TODO lor error
            return false;
        }
        return true;
    }

    public static bool RemoteServerCertificateValidationCallback(Object sender, X509Certificate certificate, X509Chain chain, SslPolicyErrors sslPolicyErrors)
{
    if (sslPolicyErrors == SslPolicyErrors.None)
        return true;

    // if got an cert auth error
    if (sslPolicyErrors != SslPolicyErrors.RemoteCertificateNameMismatch) return false;
    const string sertFileName = "smpthost.cer";

    // check if cert file exists
    if (File.Exists(sertFileName))
    {
        var actualCertificate = X509Certificate.CreateFromCertFile(sertFileName);
        return certificate.Equals(actualCertificate);
    }

    // export and check if cert not exists
    using (var file = File.Create(sertFileName))
    {
        var cert = certificate.Export(X509ContentType.Cert);
        file.Write(cert, 0, cert.Length);
    }
    var createdCertificate = X509Certificate.CreateFromCertFile(sertFileName);
    return certificate.Equals(createdCertificate);
}

}

接受的答案中的代码帮助我调试问题。然后我意识到证书参数的SN字段与我认为的SMTP服务器不相同。通过将SmtpClient实例的Host属性设置为证书的SN值，我能够解决这个问题。

我知道我在这个游戏中已经很晚了，但我还没有看到指向系统的答案。TLS流的诊断日志。

在对代码进行任何更改之前，请确保您了解问题所在。AuthenticationException是一种非常通用的异常，它没有透露太多信息。要了解底层的工作原理，请编辑应用程序的app.config文件(或创建一个新文件)，并确保拥有System。在系统中启用网络跟踪源。诊断部分，例如:

<?xml version="1.0" encoding="utf-8" ?>
<configuration>
  <system.diagnostics>
    <trace autoflush="true" />
    <sharedListeners>
      <add name="file" initializeData="c:\network.log" type="System.Diagnostics.TextWriterTraceListener" />
    </sharedListeners>
    <sources>
      <source name="System.Net" switchValue="Verbose">
        <listeners>
          <add name="file" />
        </listeners>
      </source>
    </sources>
  </system.diagnostics>
</configuration>

重新运行应用程序并检查c:\network.log文件。您应该会看到关于TLS (SSL)连接的详细信息，例如:

System.Net Information: 0 : [12764] InitializeSecurityContext(credential = System.Net.SafeFreeCredential_SECURITY, context = f44368:535f958, targetName = localhost, inFlags = ReplayDetect, SequenceDetect, Confidentiality, AllocateMemory, InitManualCredValidation)
System.Net Information: 0 : [12764] InitializeSecurityContext(In-Buffers count=2, Out-Buffer length=0, returned code=OK).
System.Net Information: 0 : [12764] Remote certificate: [Version]
  V3

[Subject]
  CN=test
  Simple Name: test
  DNS Name: example.com

[Issuer]
  CN=Root CA
  Simple Name: Root CA
  DNS Name: Root CA

...

[Signature Algorithm]
  sha256RSA(1.2.840.113549.1.1.11)

[Public Key]
  Algorithm: RSA
  Length: 2048
  Key Blob: ....
System.Net Information: 0 : [12764] SecureChannel#38496415 - Remote certificate has errors:
System.Net Information: 0 : [12764] SecureChannel#38496415 -    Certificate name mismatch.
System.Net Information: 0 : [12764] SecureChannel#38496415 - Remote certificate was verified as invalid by the user.
System.Net Error: 0 : [12764] Exception in AppDomain#10923418::UnhandledExceptionHandler - The remote certificate is invalid according to the validation procedure..

知道了问题的原因，您应该能够解决它，或者至少缩小您的谷歌搜索范围。