CuO/C microspheres are prepared by calcining CuCl2/resorcinol-formaldehyde (RF) gel in argon atmosphere followed by a subsequent oxidation process using H2O2 solution. The microstructure and morphology of materials are characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), and transition electron microscopy (TEM). Carbon microspheres have an average diameter of about 2μm, and CuO particles with the sizes of 50–200nm disperse in these microspheres. The electrochemical properties of CuO/C microspheres as anode materials for lithium ion batteries are investigated by galvanostatic discharge–charge and cyclic voltammetry (CV) tests. The results show that CuO/C microspheres deliver discharge and charge capacities of 470 and 440mAhg−1 after 50 cycles, and they also exhibit better rate capability than that of pure CuO. It is believed that the carbon microspheres play an important role in their electrochemical properties.