Rechargeable aqueous zinc-ion batteries are recently gaining incremental attention because of low cost and material abundance, but their development is plagued by limited choice of cathode materials with satisfactory cycling performance. Here, we report a porous V2O5 nanofibers cathode with high Zn-storage performance in an aqueous Zn(CF3SO3)2 electrolyte. We propose a reaction mechanism based on phase transition from orthorhombic V2O5 to zinc pyrovanadate on first discharging and reversible Zn2+ (de)intercalation in the open-structured hosts during subsequent cycling. This open and stable architecture enables a high reversible capacity of 319 mAh g−1 at 20 mA g−1 and a capacity retention of 81% over 500 cycles. The remarkable electrochemical performance makes V2O5 a promising cathode for aqueous zinc-ion batteries.