Besides drinking it. Obvi.
Shampoo with it.
Add an ounce to your bottle of shampoo to fight oil buildup. (And don't worry; since vodka is odorless, you won't walk into work smelling like a bar.)
Make your flowers last longer.
Here's something I'm going to do to my vase of peonies as soon as I get home: Add a few drops of vodka and a teaspoon of sugar to the water in your flower vase.
Painlessly remove a Band-Aid.
Take a cotton ball and soak it with vodka, then saturate the bandage; the vodka will dissolve the adhesive.