Ni foam supported-Co3O4nanowire arrays are prepared by a template-free growth method, followed by a thermal treatment in air, and are characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, infrared spectroscopy, and thermogravimetric and differential thermal analysis. The Co3O4nanowires have a diameter of about 250 nm, a length up to 15 μm, and a Brunauer-Emmett-Teller surface area of 78.4 m2g−1. They grow almost vertically from the surface of Ni foam skeleton, pack densely, and uniformly cover the entire surface of Ni foam skeleton. Electroreduction of H2O2on Co3O4nanowire arrays in alkaline medium is investigated by cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy. The Co3O4nanowire electrode exhibits superior activity, stability, and mass transport property for H2O2electroreduction. A current density of 90 mA cm−2is achieved at −0.4 V in 0.4 mol dm−3H2O2and 3.0 mol dm−3NaOH at room temperature. The per gram current density measured at −0.4 V on Co3O4nanowires is about 1.5 times of that on Co3O4nanoparticles. [ABSTRACT FROM AUTHOR]