No, Unity mail doesn't support POP3 only IMAP4 and Hotmail doesn't support IMAP4.
The application works with any IMAP4-compatible server, but the quicklists currently work with Gmail only (so you'll have to edit the launcher if you want quicklists for a different mail service).
Source.
And from the Launchpad project page:
Mail count and notifications for Ubuntu desktop
Features:
- Works with any IMAP4-compatible server
- Multiple accounts support
- Unread messages count on the Launcher
- Unity Quicklist support (GMail URLs by default)
- Messaging Menu integration
- NotifyOSD notifications