Carbon cloth supported vanadium pentoxide (V2O5) nanoflake arrays are synthesized by a facile solvothermal deposition method. The V2O5 nanoflakes grow quasi-vertically to the carbon cloth and show a star-fruit like hierarchical structure composed of 3−4 secondary flakes with a thickness of ∼20nm. When applied as cathode material for lithium ion batteries, the V2O5 nanoflake arrays exhibit a high capacity of 292 mAh g−1 at 0.5C, and 94% capacity (275 mAh g−1) retained after 100 cycles. In addition, the V2O5 nanoflakes present an impressive high-rate capability with 62% capacity (181 mAh g−1) retention when the rate changes from 0.5C to 10C. The noticeable electrochemical performances are mainly due to the carbon cloth supported thin nanoflake array structure, which provides fast ion/electron transfer, sufficient contact between active materials and electrolyte, and alleviates the structure degradation caused by volume expansion during the cycling process.