We report layer-by-layer (LBL) assembly of graphene/carbon-coated mesoporous SnO2 spheres (Gr/C-SnO2 spheres), without binder and conducting additives, as anode materials with excellent Li-ion insertion–extraction properties. Our results indicate that these novel LBL assembled electrodes have high reversible Li storage capacity, improved cycling, and especially good rate performance, even at high specific currents. The superior electrochemical performance offered by these LBL assembled Gr/C-SnO2 spheres is attributed to the enhanced electronic conductivity and effective diffusion of Li ions in the interconnected network of nanoparticles forming the mesoporous SnO2 spheres.