这有点晚了，但如果您正在寻找像Yury这样的解决方案，下面的代码将帮助您确定问题是否与自签名证书有关，如果是，则忽略自签名错误。如果需要，显然可以检查其他SSL错误。

我们使用的代码(由Microsoft - http://msdn.microsoft.com/en-us/library/office/dd633677(v=exchg.80).aspx提供)如下:

  private static bool CertificateValidationCallBack(
         object sender,
         System.Security.Cryptography.X509Certificates.X509Certificate certificate,
         System.Security.Cryptography.X509Certificates.X509Chain chain,
         System.Net.Security.SslPolicyErrors sslPolicyErrors)
    {
  // If the certificate is a valid, signed certificate, return true.
  if (sslPolicyErrors == System.Net.Security.SslPolicyErrors.None)
  {
    return true;
  }

  // If there are errors in the certificate chain, look at each error to determine the cause.
  if ((sslPolicyErrors & System.Net.Security.SslPolicyErrors.RemoteCertificateChainErrors) != 0)
  {
    if (chain != null && chain.ChainStatus != null)
    {
      foreach (System.Security.Cryptography.X509Certificates.X509ChainStatus status in chain.ChainStatus)
      {
        if ((certificate.Subject == certificate.Issuer) &&
           (status.Status == System.Security.Cryptography.X509Certificates.X509ChainStatusFlags.UntrustedRoot))
        {
          // Self-signed certificates with an untrusted root are valid. 
          continue;
        }
        else
        {
          if (status.Status != System.Security.Cryptography.X509Certificates.X509ChainStatusFlags.NoError)
          {
            // If there are any other errors in the certificate chain, the certificate is invalid,
         // so the method returns false.
            return false;
          }
        }
      }
    }

    // When processing reaches this line, the only errors in the certificate chain are 
// untrusted root errors for self-signed certificates. These certificates are valid
// for default Exchange server installations, so return true.
    return true;
  }
  else
  {
 // In all other cases, return false.
    return false;
  }
}

在我们的案例中，问题是由IIS服务器证书引起的。证书的主题设置为DNS名称，用户试图通过IP地址访问网站，因此. net证书验证失败。 当用户开始使用DNS名称时，问题消失。

因此，您必须将提供者URL更改为https://CertificateSubject/xxx/xxx.application

这有点晚了，但如果您正在寻找像Yury这样的解决方案，下面的代码将帮助您确定问题是否与自签名证书有关，如果是，则忽略自签名错误。如果需要，显然可以检查其他SSL错误。

我们使用的代码(由Microsoft - http://msdn.microsoft.com/en-us/library/office/dd633677(v=exchg.80).aspx提供)如下:

  private static bool CertificateValidationCallBack(
         object sender,
         System.Security.Cryptography.X509Certificates.X509Certificate certificate,
         System.Security.Cryptography.X509Certificates.X509Chain chain,
         System.Net.Security.SslPolicyErrors sslPolicyErrors)
    {
  // If the certificate is a valid, signed certificate, return true.
  if (sslPolicyErrors == System.Net.Security.SslPolicyErrors.None)
  {
    return true;
  }

  // If there are errors in the certificate chain, look at each error to determine the cause.
  if ((sslPolicyErrors & System.Net.Security.SslPolicyErrors.RemoteCertificateChainErrors) != 0)
  {
    if (chain != null && chain.ChainStatus != null)
    {
      foreach (System.Security.Cryptography.X509Certificates.X509ChainStatus status in chain.ChainStatus)
      {
        if ((certificate.Subject == certificate.Issuer) &&
           (status.Status == System.Security.Cryptography.X509Certificates.X509ChainStatusFlags.UntrustedRoot))
        {
          // Self-signed certificates with an untrusted root are valid. 
          continue;
        }
        else
        {
          if (status.Status != System.Security.Cryptography.X509Certificates.X509ChainStatusFlags.NoError)
          {
            // If there are any other errors in the certificate chain, the certificate is invalid,
         // so the method returns false.
            return false;
          }
        }
      }
    }

    // When processing reaches this line, the only errors in the certificate chain are 
// untrusted root errors for self-signed certificates. These certificates are valid
// for default Exchange server installations, so return true.
    return true;
  }
  else
  {
 // In all other cases, return false.
    return false;
  }
}

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。

使用我的功能诊断证书问题-见屏幕

            System.Net.ServicePointManager.ServerCertificateValidationCallback = Function(s As Object,
                                                                                          cert As System.Security.Cryptography.X509Certificates.X509Certificate,
                                                                                          chain As System.Security.Cryptography.X509Certificates.X509Chain,
                                                                                          err As System.Net.Security.SslPolicyErrors)
                                                                                     Return True
                                                                                 End Function

警告:不要在产品代码中使用此代码!

作为一种解决方法，您可以关闭证书验证。只有在确认由于错误的证书而引发错误时才这样做。

在调用smtpclient.Send()之前调用这个方法:

[Obsolete("Do not use this in Production code!!!",true)]
static void NEVER_EAT_POISON_Disable_CertificateValidation()
{
    // Disabling certificate validation can expose you to a man-in-the-middle attack
    // which may allow your encrypted message to be read by an attacker
    // https://stackoverflow.com/a/14907718/740639
    ServicePointManager.ServerCertificateValidationCallback =
        delegate (
            object s,
            X509Certificate certificate,
            X509Chain chain,
            SslPolicyErrors sslPolicyErrors
        ) {
            return true;
        };
}