The structure design of SnO2-based anode material is crucial for the development of high-performance lithium-ion batteries (LIB). Here, a solvent-evaporation induced codeposition of monodispersed polystyrene (PS) microspheres (241nm) and γ-radiation reduced graphene oxide (rGO) at the presence of the surfactant, cetyltrimethylammonium bromide (CTAB), has been firstly conducted to prepare a self-stand PS/rGO composite template film, which can transform into a porous SnO2/rGO composite material after being infiltrated with the precursor of SnO2 and further calcinated at 420°C. TGA, SEM, TEM, and nitrogen adsorption-desorption isotherms analyses indicate that the prepared SnO2/rGO composite material has 52.1wt% of rGO, and a hierarchical pore structure, i.e., mesopores (3.312nm) and macropores (∼200nm) coexist. The half-cell using the hierarchical porous structured SnO2/rGO composite as the electrode exhibits an excellent cycle performance (850mAhg−1 in 100 cycles at a current density of 0.3C) and rate property of 436mAhg−1 at a current density of 4.5C. This work indicates that the incorporation of graphene-based materials into hierarchical porous SnO2 matrix will be a potential way to obtain high-performance LIB anode material.