Sandwich structured graphene modified TiO2 mesoporous single crystals (GR-MSCs) were obtained by using the graphene embedded silica spheres as the hard template, via a hydrothermal treatment. The selective photocatalysis of TiO2 can be achieved by controlling the location of graphene in TiO2 mesoporous single crystals. The sandwich structured graphene-TiO2 composite has a photooxidation surface, and the core-shell structured TiO2@graphene has a photoreduction surface. It provides a new pathway to realize the selectivity of photocatalysis by controlling the location of graphene in TiO2 MSCs for the first time.