TiO2 nanoparticles supported on a mesoporous silica surface (TiO2/MCM-41) were selectively coated with graphene through the formation of surface complexes between TiO2 nanoparticles and 2,3-dihydroxynaphthalene and following carbonization under N2 flow. The pore structure as well as the high surface area of MCM-41 was retained even after carbonization at 1073 K. The selective graphene coating led to the enhancement of photocatalytic activities of TiO2/MCM-41 for the decomposition of 2-propanol in water compared with unmodified samples due to the appropriate adsorption properties of organics to transfer to the surface of TiO2 nanoparticles.