To further improve the electrocatalytic activity and stability of PbO2 electrode in refractory organic pollutants treatment, Fe and Ce co-doped Ti/TiO2 nanotube (TNTs)/PbO2 electrode was successfully synthesized by pulse electrodeposition. The morphology, crystallinity and elemental composition Ti/TNTs/Fe-Ce-PbO2 electrodes were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry (CV), linear sweep voltammetry (LSV) and electrochemical impendence spectroscopy (EIS) were utilized to investigate the electrochemical performance of electrodes. Results showed that Ti/TNTs/Fe-Ce-PbO2 electrodes (P) possessed finer grain size and higher specific surface than other three PbO2-based electrodes. The electrochemical measurements showed that Ti/TNTs/Fe-Ce-PbO2 electrodes (P) exhibited higher oxidation peak current, oxygen evolution potential and strong capability of center dot OH generation than those of other three kinds of electrodes. The experiments on degradation of methylene blue (MB) also indicated that Ti/TNTs/Fe-Ce-PbO2 electrodes (P) have higher chemical oxygen demand (COD) removal efficiency and instantaneous current efficiency (ICE) than the Ti/TNTs/Fe-Ce-PbO2 electrodes (D). Meanwhile, high reusability and safety were achieved by Ti/TNTs/Fe-Ce-PbO2 electrodes (P) when treating wastewater containing organic dyes.