Nano-structured vanadium oxide (V₂O₅) is fabricated via a facile thermal-decomposition of vanadium precursor, vanadyl oxalate, which is produced by reacting micro-sized V₂O₅ with oxalic acid. The V₂O₅ nanoparticles produced by this method exhibit much better electrochemical performance than commercial micro-sized V₂O₅. The optimized-nanorod electrodes give the best specific discharge capacities of 270 mAh g⁻¹ at C/2 (147 mA g⁻¹) coupled with good cycle stability with only 0.32% fading per cycle. Even at a high rate of 4C (1176 mA g⁻¹), the nanorod electrode still delivers 198 mAh g⁻¹. These results suggest that the well-separated V₂O₅ nanorod is a good cathode material for high-rate lithium battery applications.