One of the most requested questions over the internet are the POP3 and SMTP settings for Hotmail, so that arbitrary mail clients and portable devices could be used to access Windows Live Hotmail.
Until now the answer has been "there aren't any officially supported". That's changed, And it's about time. Microsoft recently, finally, enabled POP3 and SMTP access to Hotmail accounts!
In Outlook Express click on the Tools menu, Accounts... menu item, the Add button, and then the Mail... item. That should get you here:

Enter the name you would like displayed along side your email address on outgoing messages and click Next.

Enter your Hotmail email address and click Next.

Make sure that "My incoming mail server is a POP3 server" is selected, and enter:
pop3.live.com for the Incoming mail server
smtp.live.com for the Outgoing mail server
Click Next.

Enter your full Hotmail email address as the Account name, and your Windows Live Hotmail password as the Password. Click Next.

At this point Outlook Express will tell you that you are done, but in fact you are not. There are additional steps required. Go ahead and click Finish.
You should be left at your Internet Accounts dialog box:

Click on the newly created account, and then click on the Properties button.
In the resulting Properties dialog box, click on the Advanced tab.

Make sure that both cases of "This server requires a secure connection (SSL)" are checked. At that point the server port numbers should be 25 for SMTP, and 995 for POP3.
If you want: check "Leave a copy of messages on server". If you leave this unchecked mail will be downloaded or moved to Outlook Express and will not be visible on the Hotmail web interface. If you check it, then messages will be available in both places (but you'll have to delete in both places as well).
Now click on the Servers tab.

Under "Outgoing Mail Server" make sure that My server requires authentication is checked. (You can also double-check the Settings button, but the default of "Use same settings as my incoming mail server" is correct.)
That's it!
Go check for new mail in Outlook Express, or whatever email program you did this with, and you should be good to go.
(When I did this it did appear to work very slowly, and perhaps even have some limitations on the number of messages downloaded. But it's a start.)
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