Magnetron sputtered CuO thin films with hierarchical structure and large specific surface were prepared, and their electrochemical properties and reaction characteristics as the Li-ion storage electrodes were investigated. The nanostructured CuO thin film showed a high capacity, good cycling stability and excellent rate performance, exhibited the discharge capacities of 703 mAh/g at 100 mA/g and 465 mAh/g at 1000 mA/g even after 100 electrochemical cycles. Transmission electron microscopy was applied to investigate the phase evolution of CuO thin film after being electrochemically induced at various stages in the 3 rd lithiation-delithiation cycle. An intermediate phase of Cu 4 O 3 , besides Cu and Cu 2 O products, was identified in CuO electrode during the electrochemical process. The investigation of phase evolution revealed that the CuO active materials were partially reduced to Cu 4 O 3 , followed by being reduced to Cu 2 O and Cu during the discharge process; while, the reversible electrochemical reactions Cu→Cu 2 O→Cu 4 O 3 →CuO took place in the charge process.