The comparison studies on performance differences between traditional Ti-based electrode of Ti/SnO2+Sb2O4/PbO2 and novel Ti/Al composited substrate electrode of Ti/Al/Ti/SnO2+Sb2O4/PbO2 were provided. Through changing the sintering temperature of Ti/Al composited substrate, the optimum process conditions for preparing this novel electrode were obtained. The structure and morphology of Ti/Al bonding interface layers and active surface β-PbO2 coatings were characterized by SEM, EDS and XRD. Combined with electrochemical testing technology, the effect of sintering temperature on electrochemical properties and lifetime was analyzed. The results show that this novel Ti/Al composited substrate electrode, whose electrical resistivity is only one tenth of pure Ti substrate, exhibits a smaller grain size, larger surface active areas and better electrochemical properties compared to pure Ti-based electrode. Intermetallic of TiAl3 in Ti/Al composite interface is obtained at the sintering temperature of 540 °C, and it exhibits the best performance. The polarization resistance and polarization potential of Ti/Al composited substrate electrodes decline by 43% and 18%, respectively. The potential decreases by 320 mV compared to Ti-based electrode under the condition of 0.2 A/cm2 current density. This electrode has the best exchange-current density j0 and the lowest oxygen overvoltage η by strong polarization measurement. And the industrial service lifetime of this novel electrode reaches 10.4 years, 50% higher than that of traditional Ti-based electrodes