One-dimensional (1D) nanostructures of vanadium pentoxide (V2O5) have been successfully synthesized via a precipitation process followed by heating in vacuum at 300°C. The samples have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and electrochemical testing by techniques such as cyclic voltammetry (CV) and discharge–charge cycling in lithium cells. Average crystal size of these oxides increased from 36 to 83nm as annealing time was increased from 45min to 1h, which also led to a decrease in Brunauer–Emmett–Teller (BET) specific surface area from 41 to 17m2 g−1. Good cyclability and high capacity (>200mAhg−1) were achieved in the voltage range of 2.0–4.0V (versus Li metal) at a current rate of 50mAg−1 by annealing the oxides for 1h. The increase in crystallinity and higher yield of one-dimensional nanostructure oxides contributed significantly to the improved capacity and enhanced cycle life.