Anatase TiO2 nanosheets supported on reduced graphene oxide (RGO) were synthesized via a one-step, solvothermal method. During the solvothermal step, graphene oxide (GO) was reduced to RGO, and, subsequently, anatase TiO2 with 73.7% exposed {001} facets was grown in situ on the surfaces of the RGO nanosheets. Compared with pure TiO2, the RGO/TiO2 hybrid nanocomposite had improved photoactivity as a result of effective photoinduced electron transfer from TiO2 to the RGO acceptor through interfacial interactions. Trapping tests showed that the oxidation of dye molecules proceeded for about 22% through the reaction with (•)OH radicals, and the remaining 78% occurred via direct interactions with holes. The holes left in TiO2 crystals were the main reason for the enhanced photocatalytic properties of the RGO/TiO2 composite. This paper not only reports the fabrication of highly active photocatalysts but also gives deeper insight into the photocatalytic mechanism of carbon/TiO2 composites.