Various structured PbO2 electrodes were prepared by surfactant-assisted anodic electrodeposition method. PbO2-PEG thin-film electrode is composed of small particles and shows a smooth surface. PbO2-PVA electrode displays a unique structure in which the PbO2 particles are embed in the PVA network structure. PbO2-AOT electrode consists of bull-horn like particles. The morphologies and structures of PbO2 electrodes are highly influenced by the surfactant. PEG and PVA can decrease the particle size of PbO2 particle and AOT can dramatically alter the morphology of PbO2 particle. PbO2 -PEG, PbO2-PVA, and PbO2-AOT electrodes exhibit excellent electrocatalytic activity, stability, corrosion resistance, and long service life compared with bare PbO2 electrode. This work demonstrates the relationship between the structure and electrochemical performances of PbO2 electrodes, and provides a feasible approach to fabricate stable structured electrode.