The effect of bismuth (Bi) for both VO2 +/VO2+ and V3+/V2+ redox couples in vanadium flow batteries (VFBs) has been investigated by directly introducing Bi on the surface of carbon felt (CF). The results show that Bi has no catalytic effect for VO2 +/VO2+ redox couple. During the first charge process, Bi is oxidized to Bi3+ (never return back to Bi metal in the subsequent cycles) due to the low standard redox potential of 0.308V (vs. SHE) for Bi3+/Bi redox couple compared with VO2 +/VO2+ redox couple and Bi3+ exhibit no (or neglectable) electro-catalytic activity. Additionally, the relationship between Bi loading and electrochemical activity for V3+/V2+ redox couple was studied in detail. 2wt% Bi-modified carbon felt (2%-BiCF) exhibits the highest electrochemical activity. Using it as negative electrode, a high energy efficiency (EE) of 79.0% can be achieved at a high current density of 160mA/cm2, which is 5.5% higher than the pristine one. Moreover, the electrolyte utilization ratio is also increased by more than 30%. Even the cell operated at 140mA/cm2 for over 300 cycles, the EE can reach 80.9% without obvious fluctuation and attenuation, suggesting excellent catalytic activity and electrochemical stability in VFBs.