Hollow V2O5 microspheres were successfully synthesized by a solvothermal method and subsequent calcination. The rigid hollow V2O5 cathode prepared in isopropanol solvent exhibited excellent cycling performance and rate capability. Within a voltage window of 2.5 to 4 V, a maximum specific discharge capacity of 128 mA h g−1 was delivered at 1 A g−1. Even after 500 cycles, the capacity retention was 92.2%.published_or_final_versio