The porous Ti/Sb-SnO2/Ni-Ce-PbO2 electrode was prepared by using a porous Ti plate as a substrate, an Sb-doped SnO2 as an intermediate, and a PbO2 doped with Ni and Ce as an active layer. The surface morphology and crystal structure of the electrode were characterized by scanning electron microscope(SEM), energy dispersive spectrometer(EDS), and X-Ray diffraction(XRD). The electrochemical performance of the electrodes was tested by linear sweep voltammetry (LSV), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and electrode life test. The results show that the novel porous Ni-Ce-PbO2 electrodes with larger active surface area have better electrochemical activity and longer electrode life than porous undoped PbO2 electrodes and flat Ni-Ce-PbO2 electrodes. In this work, the removal of Cl− in simulated wastewater on three electrodes was also studied. The results show that the removal effect of the porous Ni-Ce-PbO2 electrode is obviously better than the other two electrodes, and the removal rate is 87.4%, while the removal rates of the other two electrodes were 72.90% and 80.20%, respectively. In addition, the mechanism of electrochemical dechlorinating was also studied. With the progress of electrolysis, we find that the increase of OH- inhibits the degradation of Cl−, however, the porous Ni-Ce-PbO2 electrode can effectively improve the removal of Cl−.