This paper reports on the electrochemical lithium intercalation/ deintercalation of single- crystalline V2O5 nanowires that were synthesized by a two- step approach including a hydrothermal process and a post- calcinating treatment. Techniques of X- ray diffraction, field- effect scanning electron microscopy, transmission electron microscopy, and high- resolution transmission electron microscopy were used to characterize the structure, morphology, and composition of the as- prepared nanowires. It was found that V2O5 nanowires were of high purity with the diameter of 50 - 200 nm and the length up to 100 mu m. The electrochemical lithium intercalation/ deintercalation of the V2O5 nanowires was investigated by cyclic voltammograms and galvanostatic charge- discharge methods. The results showed that the single-crystalline V2O5 nanowires exhibited high initial discharge capacity of 351 mAh g(-1), indicating their potential application as the cathode materials of rechargeable lithium- ion batteries. (c) 2006 The Electrochemical Society.