The Ti/Sb-SnO2 electrode and Ti/Sb-SnO2/Ce electrode were prepared by thermal decomposition. The surface morphology, phase composition and electrochemical performance of the electrodes were analyzed by SEM, EDS, XRD and CHI. Results show that SnO2 crystal cells form on the surface of the Ti/Sb-SnO2 electrode, while SnO2 grains are refined obviously due to the Ce modification and SnO2 diffraction peaks becomes stronger and broader. The Ti/Sb-SnO2/Ce electrode has the largest peak current and its surface stability and catalytic activity are enhanced greatly. Under the optimal conditions, the removal rates of orange G by Ti/Sb-SnO2/Ce, Ti/Sb-SnO2 and Ti electrodes are 94.9%, 61.9% and 46.6%, respectively, and the degradation processes follow first order reaction kinetics. The rate constants of Ti/Sb-SnO2/Ce, Ti/Sb-SnO2 and Ti electrodes are 0.1971, 0.0633 and 0.0289 min-1, respectively. The rate constant of Ti/Sb-SnO2/Ce electrode is three times of that of Ti/Sb-SnO2 electrode and seven times of that of Ti electrode. Therefore, the electro-catalytic oxidative characteristic of Ce modified Ti/Sb-SnO2 electrode is the best.