Abstract: PbO2/SPE composite membrane electrode was prepared by electroless plating directly deposited on Nafion membrane. The crystalline structure and morphology were analyzed by XRD and SEM. Results showed that the deposited layer on the membrane has a single tetragonal b-PbO2 with homogenous and dense structure and particle size of about 300－500 nm. The anodic oxygen evolution characteristic and electrolytic ozone properties of the prepared b-PbO2/SPE composite membrane electrode was investigated by using Galvanostat experiments. Compared to the other two membrane electrodes，the b-PbO2/SPE membrane electrode is more suitable as anode material for electrolytic ozone generation. Under i= 1.5 A/cm2，ozone production reached to 49.64 mg/h with current efficiency of 14.1%，bath voltage of 4.33 V and power consumption of 102.7 W·h/(g O3).