In the paper, the PbO2-Ti electrodes were characterized by SEM, and introduce the self-made catalyst Fe3+/TiO2 into the electrolytic system to treat the nitrobenzene wastewater, in order to improve the reaction speed and the removal rate of COD and NB and form heterogeneous electro-catalytic oxidation technology. In order to confirm the best removal efficiency of COD and NB, the experiment will study the electrolysis time, current intensity, pH value, and the amount of catalyst. The experimental results showed that the surface of La-doped electrode was dense and had good electro-catalytic properties.