Mesoporous flake-like β-Na0.33V2O5 has been successfully fabricated via a facile hydrothermal reaction with subsequent calcinations. The flake-like β-Na0.33V2O5 particles with an average thickness of about 100nm, are composed of small nanorods, exhibiting the mesoporous structures. The electrochemical performance demonstrate that β-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 226mA h g−1 at the current densities of 20 and 300mAg−1, respectively. The structural stability of β-Na0.33V2O5 upon cycling has been investigated by ex-situ X-ray diffraction (XRD), which indicates the β-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 β-Na0.33V2O5 material is a promising cathode material for lithium ion batteries.