Refer:
- Send same email to multiple users in ASP.Net
 
- Send EMail to multiple users records in GridView using ASP.Net
 
I have used the above link example and here is the code
protected void ExportToPDF(object sender, EventArgs e)
{
    using (StringWriter sw = new StringWriter())
    {
        using (HtmlTextWriter hw = new HtmlTextWriter(sw))
        {
            GridView1.RenderControl(hw);
            StringReader sr = new StringReader(sw.ToString());
            Document pdfDoc = new Document(PageSize.A4, 10f, 10f, 10f, 0f);
            HTMLWorker htmlparser = new HTMLWorker(pdfDoc);
            using (MemoryStream memoryStream = new MemoryStream())
            {
                PdfWriter.GetInstance(pdfDoc, memoryStream);
                pdfDoc.Open();
                htmlparser.Parse(sr);
                pdfDoc.Close();
                byte[] bytes = memoryStream.ToArray();
                memoryStream.Close();
                string receiverEmails =  this.txtEmailAddress.Text;
                MailMessage mm = new MailMessage();                    
                foreach (string email in receiverEmails.Split(','))
                {
                    mm.To.Add(email);
                }
                    
                mm.Subject = "GridView Exported PDF";
                mm.Body = this.txtMessgeBody.Text.Trim();
                mm.Attachments.Add(new Attachment(new MemoryStream(bytes), "GridViewPDF.pdf"));
                mm.IsBodyHtml = true;
                SmtpClient smtp = new SmtpClient();
                smtp.Host = "smtp.gmail.com";
                smtp.EnableSsl = true;
                System.Net.NetworkCredential NetworkCred = new System.Net.NetworkCredential();
                NetworkCred.UserName = "sender@gmail.com";
                NetworkCred.Password = "<passord>";
                smtp.UseDefaultCredentials = true;
                smtp.Credentials = NetworkCred;
                smtp.Port = 587;
                smtp.Send(mm);
            }
        }
    }
}