I looked it up and found that Higlander wheels from 2001+ share the same bolt pattern as our Rav4.2s so they will fit. Now, will the tires fit if you're buying them or taking them straight from a Highlander is another question.
Just dont get too crazy over bigger tires or bigger rims.... increase in the moment of inertia means less breaking power. The rav4's considered the best in braking in toyotas line up. I forgot where i read that from.