A novel approach for enhancing the electrochemical performance of graphite felt electrodes by employing non-precious metal oxides is designed for an all-vanadium redox flow battery (VRFB). Lead dioxide (PbO2) is prepared through pulse electrodeposition method and characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The electrochemical performance of the prepared electrode is evaluated through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Results show that PbO2 exhibits excellent electro-catalytic activity and reactive velocity to vanadium redox couples. The coulombic efficiency (CE), voltage efficiency (VE), and energy efficiency (EE) of the vanadium redox flow battery with as-prepared electrodes at 70 mA cm−2 are 99.5%, 82.4%, and 82.0%, respectively; these values are much higher than those of a cell assembled with bare graphite felt electrodes. The outstanding electro-catalytic activity and mechanical stability of PbO2 are advantageous in facilitating the redox reaction of vanadium ions, leading to the efficient operation of a vanadium redox flow battery.