Windows Live Hotmail users now can enjoy free POP3 access. Pop3 access  is not open for all countries.

POP3 technology is now available to Hotmail users in the United Kingdom, Canada, Australia, France, Japan, Spain, Germany, Italy, and the Netherlands.

Within the end of 2009 POP3 will be enabled for all countries.

Settings for POP3 Access

POP server: pop3.live.com (Port 995)
POP SSL required? Yes
User name: Your Windows Live ID, for example yourname@hotmail.com
Password: The password you usually use to sign in to Hotmail or Windows Live
SMTP server: smtp.live.com (Port 25)
Authentication required? Yes (this matches your POP username and password)
TLS/SSL required? Yes

You can use Outlook Express to connect POP3 for your hotmail account.