You have no way of knowing who is trying reset "Joe's" password. It could be Joe, or could be someone posing as Joe.
An alternative to sending an email is to either call one of Joe's phones with a one-time reset key or send an SMS message.
Calling Joe's phone with an audio message is easy with http://www.twilio.com/ But anyone might be able to pick up Joe's office phone. So usually you'd want an additional challenge before calling. Eg a secret question/answer. By using the phone and the secret q&a, you've made things tougher for the bad guys but still doable by Joe.
Another idea is to send the reset message to someone that Joe trusts and who knows Joe. (Send either by email or by telephone / sms.) A variant of this is to send to an employee who knows Joe, eg his assigned salesrep, HR rep, etc.
Use the post: Send a snail mail letter with the reset code in it. Would take a couple of days to get there, but theft of mail is a federal rap. See http://www.postalmethods.com/ If there are very bad possible negative outcomes, this can be a good solution.
For any of the above, Joe would enter the information when he sets up the account.
Another pattern is to require Joe to call into a help desk and let a human interrogate him.
Bottom line is that no technique is perfect. See the twitter breakin story: http://www.technewsworld.com/story/67612.html?wlc=1247790901&wlc=1248238327
Last thought: don't forget about anti-phishing. Often done by enabling Joe to choose a picture that the site will show him when doing something important. The idea is that a phishing site won't be able to replicate the UI, thus raising Joe's suspicions that he may not have arrived at the right site.