Individual (FTO/Cu2O and FTO/CuCo2O4) and heterostructured (FTO/BiVO4/Cu2O, FTO/BiVO4/CuCo2O4, and FTO/CuCo2O4/Cu2O) electrodes were successfully formed using the electrodeposition method on copper-containing compounds. The morphology of the synthesized electrode systems, which affect the electrochemical properties, was determined. A comparative study of the electrochemical and photoelectrochemical properties of the individual and heterostructured electrodes showed that the modification of the BiVO4 electrode surface with Cu2O and CuCo2O4 oxides led to a significant increase in its efficiency as a photoanode. The deposition of Cu2O nanoclusters onto CuCo2O4 nanoflakes increased the electrochemical stability of the electrode while maintaining its high capacitance.