I use Windows Live Hotmail mainly because most of my friends are on the Windows Live Messenger network. It is ok, with the classic version working in Opera and Safari, Full version in Internet Explorer and Firefox/Flock/Netscape. I receive quite a few emails there, mostly notifications and stuff though.
My main choice of email about be GMail, I like the web-based interface and that is my main account. I get newsletters and a lot of stuff there. The spam filter works excellent, but I'm still not comfortable with the Labels thing. I prefer folders better.
I used to use Yahoo! Mail, but the thing is, it doesn't store your message on the server after you downloaded it to POP3. GMail does, and in case of accidental deletion or Windows re-installation, I can still retrieve my emails from there. Also, Yahoo! Mail marks my emails as spam, even though it isn't. The filter is either too strict or too lenient.
More and more, I am communicating with friends through Facebook. They check that much more often than they do with Windows Live Hotmail, and it integrates really good with social networking. See this article for more information:
http://www.news.com/2009-1032_3-6197242.html.
Anyways, I would recommend GMail to new users unless they use Windows Live Messenger, then Hotmail I guess.
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