A graphite/graphite oxide (GO) composite electrode for vanadium redox battery (VRB) was prepared successfully in this paper. The materials were characterized with X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. The specific surface area was measured by the Brunauer–Emmett–Teller method. The redox reactions of [VO2]+/[VO]2+ and V3+/V2+ were studied with cyclic voltammetry and electrochemical impedance spectroscopy. The results indicated that the electrochemical performances of the electrode were improved greatly when 3wt% GO was added into graphite electrode. The redox peak currents of [VO2]+/[VO]2+ and V3+/V2+ couples on the composite electrode were increased nearly twice as large as that on the graphite electrode, and the charge transfer resistances of the redox pairs on the composite electrode are also reduced. The enhanced electrochemical activity could be ascribed to the presence of plentiful oxygen functional groups on the basal planes and sheet edges of the GO and large specific surface areas introduced by the GO.