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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.