In this work, V2O5 hollow spheres synthesized via a solvothermal method for high performance cathode of aqueous rechargeable zinc ion batteries (ARZIBs) is reported. The as-prepared V2O5 sample comprises of hollow spheres particles with diameter of 0.7–1.6 μm, which shows a larger specific area than commercial V2O5. When served as cathode of ARZIBs, V2O5 hollow spheres deliver better cycle stability and more excellent rate performance than commercial V2O5. More specifically, V2O5 hollow spheres display a high specific discharge capacity of 132 mA h g−1 with capacity retention of 82.5% after 6200 cycles at the current density of 10 A g−1. And the discharge capacity of V2O5 hollow spheres electrode can reach to 280, 250, 225, 213, 204, 165, 147 and 108 mA h g−1 at current densities of 0.2, 0.3, 0.5, 0.8, 1, 3, 5 and 10 A g−1, respectively. Further, the ZnV2O5 batteries with V2O5 hollow spheres cathode reveal a promising potential for practical application.