High-purity micro-rod β-Na0.33V2O5 particles 2⿿5μm in width and 3⿿10μm in length are prepared by the chemical switch method. Electrochemical characterization demonstrates that micro-rod β-Na0.33V2O5 as a cathode material for lithium ion batteries provides high discharge capacity, good rate-capability, and cyclic stability. It delivers high discharge capacities of 297, 245, 220, and 178mAhg⿿1 at current densities of 0.1, 0.2, 0.5, and 1C-rate, respectively. The capacity fading rate is less than 1% per cycle, with high volumetric discharge capacities (504mAhcm⿿3 at 0.1C and 301mAhcm⿿3 at 1C). Scanning electron microscopy images of the micro-rods during cycling indicate that they have excellent crystal structural reversibility in the voltage range of 1.5⿿4.0V. These superior electrochemical properties are attributed to the tunneled crystal structure and internal pores formed by crystal defects in the micro-rods.