To improve the electrochemical activity of polyacrylonitrile (PAN)-based electrospun carbon nanofibers (ECNFs) toward vanadium redox couples, the multi-wall carbon nanotubes (CNTs) and Bi-based compound as electrocatalyst have been embedded in the ECNFs to make composite electrode, respectively. The morphology and electrochemical properties of pristine ECNFs, CNTs/ECNFs and Bi/ECNFs have been characterized. Among the three kinds of electrodes, the CNTs/ECNFs show best electrochemical activity toward VO2+/ VO 2 + redox couple, while the Bi/ECNFs present the best electrochemical activity toward V2+/V3+ redox couple. Furthermore, the high overpotential of hydrogen evolution on Bi/ECNFs makes the side-reaction suppressed. Because of the large property difference between the two composite electrodes, the CNTs/ECNFs and Bi/ECNFs are designed to act as positive and negative electrode for vanadium redox flow battery (VRFB), respectively. It not only does improve the kinetics of two electrode reactions at the same time, but also reduce the kinetics difference between them. Due to the application of asymmetric electrodes, performance of the cell is improved greatly.