The Ti/SnO2-Sb2O5/PbO2 electrode was prepared by electrodeposition method onto Ti substrate with SnO2-Sb2O5 interlayer. Microstructure information of SnO2-Sb2O5 interlayer and PbO2 coating was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Our study shows that the titanium substrate is completely covered by the SnO2-Sb2O5 solid solution interlayer and the interlayer combines the Ti substrate closely with the PbO2 coating. The electrochemical performance of the Ti/SnO2-Sb2O5/PbO2 electrode was studied by cyclic voltammogram (CV), electrochemical impedance spectroscopy (EIS) and accelerated life test. The results show the electrochemical activity, electrical conductivity and stability of Ti-substrate lead dioxide electrode are increased. The deactivation process of the Ti/SnO2-Sb2O5/PbO2 electrode was also studied by the EIS. The SnO2-Sb2O5 interlayer can effectively prevent the growth of a TiO2 insulating layer between the substrate and the PbO2 coating during the lifetime tests, thus maintain high activity of Ti/SnO2-Sb2O5/PbO2 electrode for 10 times longer than Ti/PbO2 electrode without interlayer.