Provided is a photoelectrochemical electrode for carbon dioxide conversion. The photoelectrochemical electrode includes a conducting substrate and CuFeO2/CuO as a p-type copper-iron composite oxide electrodeposited on the conducting substrate. Upon irradiation, the photoelectrochemical electrode generates electrons and converts carbon dioxide to formate with a selectivity of 90 to 99%. Also disclosed is a photoelectrochemical device including the photoelectrochemical electrode.