A nanosphere array PbO2 electrode was constructed on as-prepared stainless steel-based grid-like ZnO film via anodic oxidation in lead nitrate solution. The above grid-like ZnO film was prepared in zinc nitrate solution by electrodeposition using polystyrene (PS) microsphere templates. The morphology and composition were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The performance was investigated using cyclic voltammetry (CV), linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) measurements. The results showed that the active layer of the array PbO2 electrode possesses a regular petal-like array structure that consists of many clustered PbO2 nanospheres. The array structure can increase the electrochemical active surface area (ECSA). The total voltammetric charge (qT*) is 2.6 times that of the traditional PbO2 electrode. Additionally, the array electrode shows a larger exchange current density (i0), lower activation energy (Ea) and charge transfer resistance (Rct) during the process of oxygen evolution. In the degradation process of phenol, the degradation rate constant of the array PbO2 electrode is significantly greater than that of a traditional PbO2 electrode. The results demonstrated that the array PbO2 electrode with enhanced electrocatalytic performance is a promising material for degrading organic effluents.