Co3O4 nanowires have been successfully synthesized on nickel foam by a hydrothermal method. The morphology of Co3O4 is examined by scanning and transmission electron microscopy and the phase structure of Co3O4 nanowires is confirmed by X-ray diffraction. The electrochemical capacitance behavior of the Co3O4 nanowires electrode is investigated by cyclic voltammetry, galvanostatic charge/discharge test and electrochemical impedance spectroscopy in 6moldm−3 KOH solution. The results show that the Co3O4 nanowires have diameters of around 100nm and the lengths up to 1–2μm. The specific capacitance of Co3O4 nanowires is 1019.58Fg−1 at 3.38Ag−1 and 466.06Fg−1 at 33.80Ag−1. The capacitance loss is less than 5% after 1000 charge/discharge cycles at 3.38Ag−1 and with columbic efficiency higher than 98%. The enhancement of pseudocapacitive properties at a higher charging/discharging rate is due to the porous nanostructure and the high utilization of active material.