Mesoporous flake-like beta-Na-0.33 V2O5 has been successfully fabricated via a facile hydrothermal reaction with subsequent calcinations. The flake-like beta-Na0.33V2O5 particles with an average thickness of about 100 nm, are composed of small nanorods, exhibiting the mesoporous structures. The electrochemical performance demonstrate that beta-Na0.33V2O5 with 3D tunneled crystal structure has high specific discharge capacity, good rate capability and cyclic stability. It delivers high specific discharge capacities of 339 and 226 mA h g(-1) at the current densities of 20 and 300 mA g(-1), respectively. The structural stability of beta-Na0.33V2O5 upon cycling has been investigated by ex-situ X-ray diffraction (XRD), which indicates the beta-Na0.33V2O5 has excellent crystal structural reversibility in the voltage range of 1.5-4V. Considering its surprising distinct plateaus and excellent structural stability, the beta-Na0.33V2O5 material is a promising cathode material for lithium ion batteries. (C) 2014 Elsevier Ltd. All rights reserved.