While the @hotmail.com is offered to all markets, the @live.com mail ID is not offered in all markets. This post will tell you how to create a @live.com email address.
In India for example one is offered only the hotmail.com, hotmail.co.in and live.in accounts.
But if you wish to create a @live.com mail ID, simply click on this Live.com link.
You will be taken to this page which will ask you select a language.
Selecting a language, offers you the country-specific mail IDs.
Select the language as English. Click Save.
The page you will be transferred to will offer you the @live.com mail ID.
UPDATE: Microsoft appears to have now stopped offering new @msn.com as well as live.com mail ID’s.