V2O5 nanostructures have been synthesized through an environmental friendly and simple solvent-free solid-state chemical reaction. By changing the calcination temperature in air, V2O5 nanostructures with different morphologies, such as hierarchical nanosheets, nanosheets, and hierarchical nanobelts, have been obtained. Electrochemical testing results show that hierarchical V2O5 nanobelts exhibit high specific discharge capacity and excellent cycle stability, which display high discharge specific capacities of 240mAhg−1 at 1C, whereas high discharge specific capacities of 174mAhg−1 at 8C. The delivered capacity at 1C can maintain 91% of its initial capacity (the 2nd cycle) after 100 cycles. The V2O5 nanobelts show good electrochemical performance due to its special hierarchical structure that reduces the contact resistance between the ions and materials, adjust the volume change, and relieve the pressure of large deformation in the charging/discharging process. The hierarchical V2O5 nanobelts display promising application prospects as an excellent cathode material for lithium ion batteries.