A novel carbon paper electrode coated with supported tungsten trioxide is developed to improve the carbon fiber’s electrochemical performance toward the vanadium redox couples. Super activated carbon supported tungsten trioxide (WO3/SAC) is prepared via an impregnation method and characterized by X-ray diffraction and scanning electron microscopy. The electrochemical performance of the prepared electrode is evaluated with cyclic voltammetry and electrochemical impedance spectroscopy. Results show that WO3/SAC exhibits excellent electro-catalytic activity and kinetic reversibility toward the vanadium redox couples. By adding the WO3/SAC, the charge transfer resistances for both the positive and the negative reactions are significantly reduced. Using as prepared electrodes, the columbic efficiency (CE), voltage efficiency (VE) and energy efficiency (EE) of the vanadium redox flow battery at 50 mA cm−2 are 94.5%, 85.2% and 80.5%, respectively, which are much higher than that of the cell assembled with pristine carbon paper electrodes.