Microspheres composed of multilayer graphene (MMG) had been prepared by the chemical reduction of graphene oxide at 100°C. The morphology, structure and electrochemical performance of MMG as anode material for lithium-ion batteries were investigated by high-resolution transmission electron microscope, scanning electron microscope, X-ray diffraction, X-ray photoelectron spectroscopy and electrochemical testing techniques. It is found that the specific capacity of MMG (453mAhg−1) is almost twice that of multilayer graphene (MG, 229mAhg−1). Furthermore, MMG exhibits good cycle performance and high-rate charge/discharge properties.