Piedmon
Saiyajin Quaterback
Expert doesn't equal to master, which would most accurately describe Wolverine. Good though Starfire doubtlessly is, there are two factors to consider:
1. Wolverine has had much longer than is afforded in a human lifetime to accrue skills and techniques.
2. He has adamantium claws.
No armor, and certainly not her bare hands, is going to save Starfire from Wolverine's claws. Unless she can zip out of the way, she's going down.
There are basically two scenarios (off the top of my head) where Wolverine can win.
1. They are in an enclosed chamber, something around the area of ten yards or less apart. I believe Wolverine could clear that distance and make his strike before Star could so much as power up her energy bolts. Remember, the Canuck outpaces tigers and bobcats just for training. He's faster than a jungle cat.
2. Starfire is, for whatever reason, flying low, and Wolverine has snuck up onto the pricepiece of some ledge above her. His training as a government operative allows him to move with the utmost stealth, and since Tamaranians don't possess enhanced senses Star is unlikely to notice him until it's too late. Wolverine could pounce right onto her back and finish the fight with one swipe.
Those are pretty much the only ways I can see Wolverine winning. (And obviously, neither of these totally clinch it since there's always the chance Star gets lucky and blasts him before he gets too close.)