Porous carbon derived from fungi (FDC-K) was prepared by two-step treatments including hydrothermal treatment followed by high-temperature pyrolysis with KOH, and served as electrocatalyst toward VO2+/VO2+ redox reaction for vanadium redox flow battery (VRFB). The as-prepared FDC-K is mainly microporous with large BET surface area up 1412.7 m(2) g(-1). Moreover, FDC-K is functionalized by oxygen-containing groups from KOH treatment. Water contact angle measurement confirms the outstanding wettability of FDC-K. These three characteristics are beneficial for the electrode process of VO2+/VO2+ reaction. In comparison with direct-carbonization carbon and two-step carbon without KOH activation, FDC-K shows superior electrocatalytic properties. VO2+/VO2+ couple exhibits improved electrochemical activity and reversibility on FDC-K. The charge-discharge performance of the cell using FDC-K as positive catalyst shows that using FDC-K can increase the utilization rate of active species and capacity retention. After 50 cycles at 50 mA cm(2) , the capacity retention for FDC-K can keep 78.1%, 15.4% larger than that for the pristine one. Moreover, the corresponding energy efficiency increases by 5.8% after using FDC-K. Our study reveals that fungi-derived porous carbon is an excellent electrocatalyst for VO2+/VO2+ reaction, showing the promising prospect in VRFB. (C) 2018 The Electrochemical Society.