There's some code on the PHP Code Exchange site, http://px.sklar.com, which attempts to confirm that a server will accept email for the address given (try the one at http://px.sklar.com/code-pretty.html?code_id=414, but there are others in the "Networking" section). I've tried a similar approach before, and had a few problems with certain addresses (particularly hotmail and AOL addresses), but the author seems to suggest that his code works under those circumstances.
If you're just looking to check whether the address is in a valid format, you could use a regular expression something like this:
eregi("0-9a-z@0-9a-z\.[a-z]{2,3}$",$email);
(I think this is right - regular expressions have never been my strong point...)
Kevin