Short answer: no.
Long answer: As his girlfriend, I think the two of your should have a level of trust and open communication that would deem this activity unnecessary. If you want to know something, for god's sake: ask him! Not to in any way suggest that I'm an expert on relationships, but I know that communication is a good thing.
However, back to the actual subject. Hotmail is a fairly secure system. If you really want to go through with this, your best bets would be to either guess his password, or take a look at his question for a forgotten password. Having said this, I have to also add that I don't endorse this. 1. It's illegal, and we all know I don't like illegal things. 2. You're going to really be violating his trust if you do this. If I found out my girlfriend suspected me of something, and then went around behind my back and hacked into my stuff...(well, first I'd be impressed with her inginuity), but I highly doubt the relationship would continue.
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