In this study, the Cu2O/CuO/Cu complex films were prepared with the copper plate as the carrier of catalyst. First, the CuO nanoribbons (CuO NRs) were developed on the copper plate by the surface oxidation method. And then the Cu2O was loaded on the CuO NRs by electrochemical methods. X-ray diffraction (XRD) and transmission electron microscope (TEM) were carried out to characterize complex films. Linear sweep voltammetry, photocurrent-time measurement and electrochemical impedance spectroscopy were used to study the photoelectrocatalytic reduction performance for CO2. The reduction product of CO2 was determined by chromotropic acid spectrophotometry method. The results showed that the CuO films were composed with nanoribbons and the Cu2O/CuO/Cu complex films had excellent photoelectrocatalytic performance. Methanol was the major product of the photoelectrocatalytic reduction of CO2 and its concentration reached 32.2μg/mL after 6h. This study has some guidance for photoelectrocatalytic CO2 reduction.