A novel of Ti/TiO2NTs/NiO/Ce-PbO2 electrode was constructed by electrodeposition technique. Characterization experiments including scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), cyclic voltammetry (CV), linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) were performed to evaluate the performance of Ti/TiO2NTs/NiO/Ce-PbO2 electrode. The results show that, compared with the Ti/TiO2NTs/PbO2 and Ti/TiO2NTs/Ce-PbO2 electrode, the novel Ti/TiO2NTs/NiO/Ce-PbO2 electrode with more compact surface and a fine grain size possessed smaller charge transfer resistance and higher oxygen evolution potential. The Ti/TiO2NTs/NiO/Ce-PbO2 had higher electrochemical activity than those of other three kinds of electrodes due to the larger electrochemical active surface area. Phenol was employed as a model organic pollutant for electrochemical degradation to evaluate the electrocatalytic activity of the novel Ti/TiO2NTs/NiO/Ce-PbO2 electrode. The removal efficiency of phenol and TOC reached 100.0% and 98.1% respectively after 180min under the optimal conditions. In addition, the degradation of phenol followed pseudo-first-order kinetics. The results demonstrated that the Ti/TiO2NTs/NiO/Ce-PbO2 with enhanced electrochemical performance is a promising material for degrading organic pollutants.