Use http://www.decolar.com for flights airlines GOL and TAM have about 12-15 flights per day between the cities. Flight is much easier more convenient than the bus but make sure to fly the domestic airports CGH (Sao Paulo) & SDU (Rio De Janeiro) as they both are located in the central part of the city much closer to your most likely final destination within each respective city.
best way to travel from Rio to Sao Paulo ?
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