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;
  }
}

检查计算机的日期和时间。如果错误，请将其更新为当前时间或自动设置为从Internet获取时间。

因为证书与固定的时间段绑定，如果您的时钟错误，您可能会得到这样的错误。在这种情况下，通过固定时间，问题将得到解决。

有一篇MSDN博客文章是关于调查这类问题的:

故障排除ASP。NET -根据验证过程，远程证书无效: http://blogs.msdn.com/b/jpsanders/archive/2009/09/16/troubleshooting-asp-net-the-remote-certificate-is-invalid-according-to-the-validation-procedure.aspx

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。

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