In this study, TiO₂ hollow microspheres with high photocatalytic activity were prepared by simply optimizing the ratio of the as-used templates (poly(4-styrenesulfonate) (PSS) and triblock copolymer P123). In particular, a novel three-dimensional (3D) reduced graphene oxide/TiO₂ (rGO/TiO₂) hybrid composite was for the first time prepared by wrapping TiO₂ hollow microspheres with rGO sheets via a facile solvothermal route using poly(L-lysine) (PLL) and ethylene glycol (EG) as coupling agents. The structural, morphological and photocatalytic properties of the as-synthesized products were examined. It is found that rGO/TiO₂ hybrid composite exhibits markedly enhanced photocatalytic performance in comparison with pure TiO₂ hollow microspheres and the simple mixture of rGO and TiO₂ spheres. The rational design, interesting structure and ideal photocatalytic performance of this graphene-based composite show great promise in diverse fields.