In this work, the Ti/PbO2 anode materials were prepared from nitrate solutions in the presence of fatty alcohol polyoxyethylene ether AEO to study the effects of AEO on PbO2 deposition. The phase composition and microstructure of electrode material were characterized by XRD and SEM. The PbO2 electrodeposition mechanism and electrocrystallization behavior were investigated by cyclic voltammetry (CV), linear sweep voltammetry (LSV), chronoamperometry (CA) and Scharifker-Hills (SH) mechanism. The results indicate that: The material is composed by beta-PbO2 in this case and the growth orientation of the crystal face is changed by AEO; The growth model of PbO2 crystals is in good agreement with Generalized Electrochemical Aggregative Growth Mechanism; The AEO can improve the morphology of PbO2 plating, and makes the surface smoother without flaws; The PbO2 electrodeposition is diffusion-irreversible-controlled process in the presence of AEO; The deposition on substrate is promoted, nevertheless, the further deposition on PbO2 coating is restrained by AEO; The D-0 at each of step potentials, which relates to diffusion coefficient, was improved by AEO revealed variation of solution nature; The electrocrystallization of PbO2 follows Scharifker-Hills(SH) progressive nucleation/growth mechanism with the oxygen evolution occurring simultaneously, and the AEO increased the number density of active sites but reduced the nucleation rate. (C) The Author(s) 2016. Published by ECS.