Boron or nitrogen mono-doped carbon nanofiber (CNF), and boron, nitrogen co-doped CNF are intentionally prepared as positive electrodes in a vanadium redox flow battery (VRFB). The structures and electrochemical properties of the materials are investigated by Scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, cyclic voltammetry and electrochemical impendence spectroscopy. The experimental results indicate that either B or N mono-doped CNF shown better electrochemical performance than untreated one. Interestingly, for the B and N co-doped CNF, the separated case exhibited an outstanding electrochemical activity better than either B or N mono-doped case, while the bonded case leading to a sharp drop in conductivity and shown poor electrochemical performances. These results demonstrated that not the total amount of incorporated B and N but how the B and N are incorporated into carbon nanostructures determines the catalytic activity toward VO2+/VO2 + reaction. Moreover, the individual mechanism of the nitrogen and boron containing functional groups act as active sites have been analyzed.