The lead dioxide electrode (PbO2) with Ti substrate and SnO2-Sb2O5 intermediate layer was doped by F- ion through the potentiostatic anode co-deposition method. The content of F in the coating can be controlled by adjusting deposition potential. The effect of F- doping on the composition, surface morphology and electrochemical properties of the PbO2 electrode was characterized by X-ray diffraction, scanning electron microscope, X-ray photoelectron spectroscopy and electrochemical measurement methods. The results have confirmed that the content of β-PbO2 increases with increasing that of F, and the doping can make the β-PbO2 grains become fine and the electrode surface become smooth; the specific surface areas and conductivity increase, and the initial potential of oxygen evolution shifts toward positive direction compared with the free-doped PbO2 electrode; the oxygen evolution potential increases with the increasing of the F-content in the PbO2 film electrode. The bulk electrolysis result demonstrated that the performances of the F-PbO2 electrode for anodic oxidation aniline have been improved to some extent. Copyright © 2012 John Wiley & Sons, Ltd.