Pure ZnO, Cu-ZnO, S-ZnO and (Cu,S) -ZnO nanoparticles were prepared by hydrothermal method. The crystal structure and surface morphology were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The electrochemical properties of electrodes were measured using an electrochemical workstation. Furthermore, the methylene blue solution was used to simulate wastewater to study its photoelectrochemical property. The results showed that the addition of dopant did not change the crystal structure, but the grain size decreased significantly, the surface area increased, and the surface distribution was more uniform. The electrocatalytic activity of the electrode is significantly increased after doping. Among them, (Cu,S)-ZnO nanoparticles has the best electrochemical properties and the highest degradation rate of methylene blue solution, up to 87.69%.