Follow the simple steps mentioned below, and you could get an @Live.com email address..
1. Right-click on this link and copy it to the clipboard. It won’t do you any good to just click on the link, you need to actually copy it to use later.
2. Go to http://get.live.com/getlive/overview in Internet Explorer and click | Sign Up | This maynot work in Firefox, suggest to use IE.
3. Paste what you just copied in step 1 into the address bar and press enter to execute it. The script adds a | Live.com | option to the drop-down menu of domain choices.
4. Fill out the rest of the details and you’re all set!
Hopefully Microsoft will release these email addresses to the public soon but they will probably wait until Windows Live Mail is officially released. So you better hurry and get the address(es) that you want before all of the good ones have been taken and they shutdown this trick!