In this paper, the Cu/Cu 2 O/CuO three-phase coexistence system was obtained by one-step electrochemical deposition method, and CuO nanowheat spike array film was successfully prepared by annealing treatment eventually. Field emission scanning electron microscopy (FESEM) was used to characterize the growth evolution of the synthesized product by adjusting the concentration of copper acetate and the deposition time. The results showed that the concentration of copper acetate plays a key effect on the morphology of the sample. X-ray diffraction (XRD) results exhibited that the synthesized samples (Cu/Cu 2 O/CuO three-phase) have good crystallinity. With the increase of annealing temperature, the sample changed from Cu/Cu 2 O/CuO three-phase to CuO single-phase gradually. In addition, the UV–Vis, Nyquist plots and photoelectrochemical analysis were employed for characterization of the samples annealed at different temperatures. These studies showed that the samples annealed at 350 ∘ C exhibit the best photoelectric properties.