The Ti 4 O 7 modified Ti/PbO 2 electrodes have been prepared by electrodeposition, and investigated systemically using scanning electron microscope (SEM), Energy dispersive X-ray spectroscopy (EDS), powder X-ray diffraction (XRD), photoluminescence spectroscopy (PL), and degradation of anthraquinone dye (reactive brilliant blue KNÀR: C 22 H 16 N 2 Na 2 O 11 S 3 ). It is found that the Ti 4 O 7 modified Ti/PbO 2 electrodes possessed smaller PbO 2 crystal grains, good porous structure, enhanced oxygen evolution over-potential and higher electrical conductivity, as compared to that of Ti/PbO 2 electrode. Additionally, the Ti 4 O 7 modified Ti/PbO 2 electrode exhibited also longer accelerated lifetime, and higher photoelectrocatalytic activity for degradation of anthraquinone dye (reactive brilliant blue KNÀR) than that of Ti/PbO 2 electrode. The enhancement of the decolorization efficiency and stability for Ti 4 O 7 modified Ti/PbO 2 electrodes can be ascribed to the large electrochemical active areas, the presence of photoelectric synergism, rapid separation of photogenerated carriers, inhibition of oxygen precipitation, high current efficiency for formation of hydroxyl radicals, and the weakening of internal stress in PbO 2 coatings.