Nanoflower-like CuO/Ni film was prepared by electrodeposition method in an alkaline nickel electroplating solution, and the nanoflower-like CuO film was obtained by direct oxidation on copper substrate. The nanoflower-like CuO was crystalline with space group of C2/c, and the amorphous Ni particle layer on the surface of film contacted well with the nanoflower-like CuO. The electrochemical properties of CuO/Ni film were investigated by cyclic voltammetry (CV) and galvanostatic charge–discharge tests. Since the metallic Ni can act as conductor and catalyst, the CuO/Ni film exhibits higher initial coulombic efficiency (72.1%) than the pure CuO film (57.0%), and better capacity retention (96.3% of the 2nd cycle) than the pure CuO film (67.8% of the 2nd cycle) at the current density of 0.1mAcm−2.