From Hotmail Help section...
To set up your Hotmail account in Outlook Express, you'll need to use Outlook Express version 5.5 or later.
In Outlook Express, click Accounts on the Tools menu.
In the Internet Accounts dialog box, click Add, and then click Mail.
On the first page of the Internet Connection Wizard, type your full name, and then click Next.
On the Internet E-mail Address page, type your full Hotmail address (name@hotmail.com).
On the E-mail Server Name page, click HTTP in the My incoming mail server is box.
In the box My HTTP service provider is, click Hotmail.
On the Internet Mail Logon page, type your password.
Click Finish to add your Hotmail account to Outlook Express.
Notes
Access to your MSN Hotmail account in Outlook Express is provided as a trial service only with limited support.
You can download the latest version of Outlook Express from the Web. For Windows, go to the Microsoft Internet Explorer Web site. For the Macintosh, go to the mactopia download Web site.
If several members of your household have Hotmail accounts, you can add those accounts to Outlook Express. Or you can create multiple identities in Outlook Express to keep each account private. On the Help menu, click Contents and Index. On the Index tab, type identities. Click an Identities subentry, and then click Display to see the topic.