The composite supercapacitor electrodes were rationally fabricated by facile electrochemical deposition of polypyrrole (PPy) on NiCo2O4 nanowire arrays which were grown radially on carbon fiber (CF). When used as electrodes in supercapacitors, the composite nanostructures demonstrated prominent electrochemical performances with a high areal capacitance (1.44 F/cm2 at a current density of 2 mA/cm2 ), a good rate capability (80.5% when the current density increases from 2 mA/cm2 to 20 mA/cm2 ), and a good cycling ability (85% of the initial specific capacitance remained after 5000 cycles at a high current density of 10 mA/cm2 ). The excellent electrochemical performance of NiCo2O4@PPy nanostructures can be mainly ascribed to the good electrical conductivity of PPy, the enhanced adherent force between electrode materials and CF to hold the electrode fragments together by means of NiCo2O4 nanowires, the short ion diffusion pathway in ordered porous NiCo2O4 nanowires and the three-dimensional nanostructures.