Microsoft made available the new Hotmail with SSL to all. To access it, simply visit this link, and upon first sign-in you'll be given a choice "Always use HTTPS", or "Continue to Hotmail" and use HTTPS for this time only.
If you prefer to choose Always use HTTPS, you'll be redirected to HTTPS address. And, to make change to your settings, simply visit here on Windows Live Account.
Note: if you choose to Always use HTTPS, will cause errors in Windows Live Mail, Outlook Hotmail Connector, as well as Windows Live for Windows Mobile and Nokia phones. Also, that bookmarking HTTPS address for Hotmail might be an easier option, while maintaining compatibility with Windows Live Mail or Outlook Hotmail Connector.