Mesoporous single-crystalline V2O5 nanorods assembled into novel hollow microspheres have been synthesized as cathode materials for lithium-ion batteries by a simple solvothermal treatment of NH4VO3 and ethylene glycol with subsequent annealing in air at 400 °C, which delivered a very high reversible capacity of 145.8 mA h g(-1) at 2.5-4.0 V (vs. theoretical value: 147 mA h g(-1)) with much improved capacity retention and long cycle life at various rates.