Make sure that you are a subscriber of Windows Live Hotmail Plus.
1. Select Tools>Account Settings (from the menu in Outlook).
2. Go to the E-mail tab.
3. Click New
4. Make sure Microsoft Exchange, POP3, IMAP, or HTTP is selected.
5. Click Next >.
6. Type your name as you want it to appear in outgoing email under Your Name
7. Enter your Windows Live Hotmail address under E-mail Address
8. Make sure that Manually configure server settings or additional server types is checked.
9. Click Next.
10. Make sure Internet E-mail is selected.
11. Click Next
12. Make sure POP3 is selected under Account Type.
13. Enter (pop3.live.com) (not including the quotation parenthesis) under Incoming mail server.
14. Type (smtp.live.com) under Outgoing mail server (SMTP).
15. Enter your complete Windows Live Hotmail address (username@hotmail.com, for example) under User Name.
16. Type your Windows Live Hotmail password under Password.
17. Click More Settings.
18. Go to the Outgoing Server tab.
19. Make sure My outgoing server (SMTP) requires authentication is checked.
20. Verify Use same settings as my incoming mail server is selected.
21. Go to the Advanced tab.
22. Make sure This server requires an encrypted connection (SSL) is checked under Incoming server (POP3).
23. Make sure SSL is selected for Use the following type of encrypted connection: under Outgoing server (SMTP)
24. Check that „995“ appears under Incoming server (POP3) and „25“ under Outgoing server (SMTP).
25. Click OK.
26. Now click Next.
27. Click Finish.