Three-dimensional V2O5 hollow structures have been prepared through a simple synthesis strategy combining solvothermal treatment and a subsequent thermal annealing. The V2O5 materials are composed of microspheres 2–3 μm in diameter and with a distinct hollow interior. The as-synthesized V2O5 hollow microspheres, when evaluated as a cathode material for lithium-ion batteries, can deliver a specific capacity as high as 273 mAh·g−1 at 0.2 C. Benefiting from the hollow structures that afford fast electrolyte transport and volume accommodation, the V2O5 cathode also exhibits a superior rate capability and excellent cycling stability. The good Li-ion storage performance demonstrates the great potential of this unique V2O5 hollow material as a high-performance cathode for lithium-ion batteries.