There are some ways that you can potentially validate an that a mail server recognizes and email address, but my understanding is that they are not by any means perfect. Some mail servers may "play along" and return the appropriate responses, but others will not, so you will likely end up with many false negatives.
The only way I know of that is at all reliable is the email confirmation method suggested above (which is why virtually all site sign-up systems use it if they want to validate that the supplied email address is valid).