We report a simple strategy to grow a novel cobalt nickel vanadium oxide (CoxNiVyOz) nanocomposite on bare and reduced-graphene-oxide (rGO)-coated nickel foam (Ni foam) substrates. In this way, the synthesized graphene oxide is coated on Ni foam, and reduced electrochemically with a negative voltage to prepare a more conductive rGO-coated Ni foam substrate. The fabricated electrodes were characterized with a field-emission scanning electron microscope (FESEM), energy-dispersive X-ray spectra (EDX), X-ray photoelectron spectra (XPS), and Fourier-transform infrared (FTIR) spectra. The electrochemical performance of these CoxNiVyOz-based electrode materials deposited on rGO-coated Ni foam substrate exhibited superior specific capacitance 701.08 F/g, which is more than twice that of a sample coated on bare Ni foam (300.31 F/g) under the same experimental conditions at current density 2 A/g. Our work highlights the effect of covering the Ni foam surface with a rGO film to expedite the specific capacity of the supercapacitors. Despite the slightly decreased stability of a CoxNiVyOz-based electrode coated on a Ni foam@rGO substrate, the facile synthesis, large specific capacitance, and preservation of 92% of the initial capacitance, even after running 5500 cyclic voltammetric (CV) scans, indicate that the CoxNiVyOz-based electrode is a promising candidate for high-performance energy-storage devices.