Developing electrode materials that can work efficiently at high current densities while maintaining excellent stability is critical for reducing the unit cost of vanadium flow batteries (VFB). Herein, we report a Bi nanoparticles (∼10 nm) decorated thermal-active graphite felt (Bi@TGF) electrode fabricated through a simple polyvinylpyrrolidone guided approach. Fine and dense Bi electrocatalysts not only play an important role in catalyzing V2+/V3+ redox reaction, but also effectively suppress hydrogen evolution side reaction. As a result, the VFB assembled with Bi@TGF as negative electrode exhibits excellent rate performance (energy efficiency of 81.5 % at 200 mA cm−2) and extremely high peak power density (1023 mW cm−2 at 1250 mA cm−2). Moreover, Bi@TGF electrode demonstrates outstanding durability in 2500-cycle ultralong charge-discharge testing at 300 mA cm−2, with energy (voltage) efficiency retention rate of 99.2 % (98.9 %). The stable cycling ability of Bi@TGF under high operating current density endows its potential application in long-duration and high power density VFB.