A new SiO2/Cu/polyacrylonitrile-C composite (donated as SiO2/Cu/PAN-C) is prepared by mechanical ball milling and heat treatment of CuO-coated SiO2 and polyacrylonitrile. During heat treatment, Cu is produced by reduction of CuO and SiO2 is embedded in the matrix of Cu and PAN-C. SiO2 in the composite presents a specific capacity of 1230 mAh g−1, and exhibits excellent cyclic stability and rate capability when cycling in the voltage range of 0.0–3.0 V. Electrochemical impedance spectra (EIS) indicate that the addition of Cu effectively improves the conductivity of electrode and diminishes interfacial impedance.