I do think it's a peculiar choice, Franco and Hathaway having no former connection whatsoever. I guess Franco's latest success with "127 hours" has done him good. And Anne being the new Catwoman supposedly made her an appropriate choice. Come to think of it, this will give me a good oppertunity to observe the Catwoman heiress a little.
Though neither of them has the gift of humor, they both imply a certain charm and wit. They'll probably do fine as long as they don't use too much (forced) jokes. Well, I guess we'll just have to wait and see.
Here's a promo featuring the two hosts: