In this work, a new electrochemical method based on fast Fourier transformation continuous cyclic voltammetry (FFTCCV) technique is introduced for electrodepositing of nano-structured PbO2. During the electrodepositing, a special potential waveform, consisted of a potential step and a potential ramp, was continuously applied on a Pt disk electrode. Various parameters such as potential scan rate, and potential of step were optimized to obtain higher capacity and stability for the formed lead oxide layer. Depend on the potential waveform condition, the morphology and connectivity of the oxide film was changed. The energy storage ability of the prepared lead acid batteries shows a close relation with the morphology of cathode materials. Maximum current efficiency was observed when the potential scan rate reaches to 5Vs−1. The electrode surface was characterized by SEM. The results showed the high surface area as well as high connectivity between particles resulted at optimum scan rate. Analysis of FFTCCV data of obtained PbO2 in H2SO4 revealed that the electrocatalytic properties, and as well stability of PbO2 layer amplified by increasing scan rates up to an optimum value. In addition, a larger over potential for oxygen evolution reaction was also observed for the electrodes by application of this method.