Instead of worrying about what email addresses can and can't contain, which you really don't care about, test whether your setup can send them email or not—this is what you really care about! This means actually sending a verification email.
Otherwise, you can't catch a much more common case of accidental typos that stay within any character set you devise. (Quick: is [email protected] a valid address for me to use at your site, or not?) It also avoids unnecessarily and gratuitously alienating any users when you tell them their perfectly valid and correct address is wrong. You still may not be able to process some addresses (this is necessary alienation), as the other answers say: email address processing isn't trivial; but that's something they need to find out if they want to provide you with an email address!
All you should check is that the user supplies some text before an @, some text after it, and the address isn't outrageously long (say 1000 characters). If you want to provide a warning ("this looks like trouble! is there a typo? double-check before continuing"), that's fine, but it shouldn't block the add-email-address process.
Of course, if you don't care to ever send email to them, then just take whatever they enter. For example, the address might solely be used for Gravatar, but Gravatar verifies all email addresses anyway.