Anatase TiO2 with {001} facets is much more active than that with {101} facets, which has been verified via experiments and theoretical calculations. Graphene has garnered much attention since it was initially synthesized, due to its unique properties. In this study, reduced graphene oxide (RGO)/{001} faceted TiO2 composites were fabricated via a solvothermal method. The composites were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectrophotometry, photoluminescence and Raman analysis. The results revealed that the graphene oxide was reduced during the preparation process of the {001} faceted TiO2, and combined with the surface of {001} TiO2. The photocatalytic activities of the composites were evaluated through the degradation of basic violet, under both white light (lambda > 390 nm) and visible light (lambda = 420 nm) irradiation. The results indicated that the photocatalytic activities of the {001} faceted TiO2 were significantly improved following the incorporation of RGO, particularly under visible light irradiation. Theoretical calculations showed that the band structure of the {001} faceted TiO2 was modified via graphene hybridization, where the separation of photoinduced electron-hole pairs was promoted; thus, the photocatalytic activity was enhanced.