The photocatalytic activity of TiO₂ is limited by the aggregation of nanoparticles and the fast electron–hole pair recombination. Graphene sheets, with high specific surface area and unique electronic properties, can be used as a good support for TiO₂ to enhance the photocatalytic activity. Herein, we prepared graphene–TiO₂ (G–TiO₂) composites through a one-pot solvothermal reaction by using graphite oxide (GO) and tetrabutyl titanate as starting materials. TiO₂ particles with anatase phase and a narrow size distribution were dispersed on the surface of graphene sheets uniformly. The fluorescence quenching confirmed that graphene acted as an electron-acceptor material to effectively hinder the electron–hole pair recombination of TiO₂. The product prepared with 30 mg of GO and 8 h of reaction time exhibited excellent photocatalysis to methylene blue (MB) degradation under irradiation of simulated sunlight. Such intriguing photocatalyst may find significant applications in various fields.