Hierarchically nanostructured materials have proven their superiority in high performance lithium ion batteries. Herein, we successfully fabricate hierarchical vanadium pentoxide (V2O5) nanobelts by an economical and facile hydrothermal strategy followed by annealing treatment. A self-template growth of hierarchical V2O5 nanobelts was achieved from precursor VO2 (B) nanobelts, resulting in open structure of hierarchical V2O5 nanobelts composed of plate-like V2O5 nanocrystals and tiny haircuts. The hierarchical nanobelts deliver a high specific surface area of 137.5m2 g−1. When used as the cathode material for lithium ion battery, the hierarchical V2O5 nanobelts exhibit high discharge capacity of 288mAhg−1, which maintain 246mAhg−1 at the end of 50th cycle with capacity retention of 85.4 %.The present electrochemical results demonstrate the high discharge capacity, superior cycling stability and rate capability of the hierarchical V2O5 nanobelts, which could be attributed to the advantages of unique hierarchical nanobelt structure.