If you mean will the e-mail address CL gave you work with Windows Live Mail, the answer is yes!
I would start here: »
internethelp.centurylink ··· ess.html and choose what your e-mail address ends in.
If your account is pretty new and you have a CenturyLink.net e-mail address, you can go right here: »
internethelp.centurylink ··· e-1.htmlIMAP would be preferable, which would be preferable, because POP deletes email from the server when it pulls it to your computer, so if your computer has a problem and you aren't running backups, or you use more than one computer or device to pull e-mail, you may lose mail.
They don't seem to "support it" but the IMAP connection information is here: »
internethelp.centurylink ··· s-1.htmlIf you're talking about using your existing live.com account, you can keep using that in the WLM application with no problems.