Herein, leaf-like CuO with mesoporous structure has been synthesized by treating commercial Cu(OH)2 powder at room temperature for an appropriate time. The BET measurement shows that the obtained CuO has a high surface area of 23.55m2 g−1 and narrow pore distribution peaking at about 3.3nm. The electrochemical performances of leaf-like mesoporous CuO are evaluated by cyclic voltammetry and galvanostatic charge-discharge studies. Electrochemical results show that the as-prepared CuO are promising anode materials in LIBs including high specific capacity, good retention and rate property. Even at the high current density of 2000mAg−1, the mesoporous CuO electrode still can maintain a specific capacity of 490.5mAhg−1 which is much higher than the theoretical specific capacity of graphite (372mAhg−1).