A novel electrochemical route to fabricate ordered mesoporous metal oxide film electrodes has been investigated with particular reference to nickel oxide. Ordered mesoporous nickel oxide films are successfully synthesized by templated electrodeposition of HI-e nickel hydroxide and followed by heat-treatment in air at various temperatures. The films are characterized physically by thermogravimetry (TG), transmission electron microscopy (TEM) and X-ray diffraction (XRD). The applicability of this film as inexpensive and high-performance supercapacitor electrode material is demonstrated by the electrochemical characterization using cyclic voltammetry (CV) and chronopotentiometry technique. The specific capacitance of the nickel oxide film depends on the annealing temperature, showing a maximum value of 590Fg−1 when the as-deposited film is heat-treated at 250°C for 1.5h.