Emailing in VB.Net is a synch. But there are some things you should be aware of.

 1. always handle errors on the send, i've never seen an app that hasn't failed email at some point in time.

2. ensure you use the Imports system.net statement at the top of your page.

3. if everything completed successfully and you didn't recieve the email you might have relaying disabled. 

 Sub Authenticate()
'create the mail message
Dim mail As New MailMessage()
'set the addresses
mail.From = New MailAddress("me@mycompany.com")
mail.To.Add("you@yourcompany.com")
'set the content
mail.Subject = "This is an email"
mail.Body = "this is the body content of the email."
'send the message
Dim smtp As New SmtpClient("127.0.0.1")
'to authenticate we set the username and password properites on the SmtpClient
smtp.Credentials = New NetworkCredential("username", "secret")
smtp.Send(mail)

End Sub 'Authenticate