You have to use "Outlook connector", which is freely available at micrsoft web site to synchronize with hotmail unless you have a paid (a.k.a premium) account. If you do have a paid account its simple. Just put ur email adderss in the relevent field and outlook will take care of the rest. Or else use the following settings if you prefer to do it manually.
Note that this works only if you have a paid hotmail account. otherwise you'll have to download outlook connector from microsoft and follow the instructions that come along with it.
In Outlook Express, on the Tools menu, click Accounts.
Click Add, and then click Mail.
Type your name, and then click Next.
Type your full Windows Live Hotmail e-mail address, and then click Next.
Enter the following information, and then click Next:
In the My incoming mail server is a box, select POP3.
In the Incoming mail (POP3, IMAP, or HTTP) server box, type pop3.live.com.
In the Outgoing mail (SMTP) server box, type smtp.live.com
Type the account name and the password for your Windows Live Hotmail account. Clear the Remember password check box unless you're the only person with access to the computer. Make sure that the Log on using Secure Password Authentication (SPA) check box isn't selected.
Click Next, and then click Finish.
In the Internet Accounts window, on the Mail tab, click the Windows Live Hotmail account that you added, and then click Properties.
On the Advanced tab, under Server Port Numbers, enter the following information, and then click OK:
In the Incoming server (POP3) box, type 995.
In the Outgoing server (SMTP) box, type 25.
Under both Outgoing mail (SMTP) and Incoming mail (POP3), select the This server requires a secure connection (SSL) check boxes.