A nickel intermediate layer was firstly electrodeposited onto the titanium substrate by cathodic electroplating, then the β-PbO2 coating was electrosynthesized by anodic oxidation. The resulting Ti/Ni/PbO2 was compared with the Ti/PbO2 electrodes without intermediate layer. The effect of plating nickel intermediate layer on the structure and performance of PbO2-coated electrodes were investigated by microstructure characterization, accelerated life test in 1mol/L H2SO4 solution, electrochemical performance and electro-oxidation behavior of simulated phenol wastewater. The results indicated that the introduction of nickel electroplating intermediate layer leads to the grain refinement of the surface active β-PbO2 coating, thus enhancing the catalytic performance of PbO2-coated electrodes. Furthermore, the Ni intermediate improves the conductivity of the electrode, thus significantly reducing cell voltage, enhancing potential uniform distribution of the electrode surface, extending the electrode lifetime and reducing the energy consumption of electrocatalytic oxidation of simulated phenol wastewater. Besides, the introduction of nickel inter-layer might enhance the catalytic performance of the electrode.