I go to Brazil about every other month and agree with Curval
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Wow you are going to rent a car? Sao Paulo and Rio are both wild places to drive. Street and highway signs are poorly marked and it's a very confusing place to drive. You can find yourself in Indian Country very quickly if you get lost. Take the wrong exit off the highway in Rio and you end up in a Favela....Indian Country...the Apaches might get you.
Why Sao Paulo? Sao Paulo is pretty much a huge, boring, industrial city. In the state of Sao Paulo get a away from the city and go to Campos de Jordao in the mountains.
http://www.camposdojordao.com.br/Rio has a lot to offer. Also be sure to visit Buzios and Angra dos Reis.
http://www.angra-dos-reis.com/ingles/This is a pretty good source for travel, booking, and tours as well. The owner is from New York and is reputable. I know him and his company has arranged several things for me.
http://www.blameitonrio4travel.com/newsite2/index.htmlAlso, don't go around Rio with anything you don't mind too badly getting robbed. I've known a lot of folks that have been robbed. Just be ready for it if it happens. Stay in groups is the most important. Use a money clip and carry no more than just what you will need. Use the hotel safe.