Details on the electrochemical formation of lead dioxide from aqueous plumbous ion are studied by measuring current-time behavior with potential step method at a rotating platinum electrode. A cubic law without induction period can be applied to the crystallization of lead dioxide in both acetate and nitrate media. In the course of the mechanistic study, the presence of a soluble intermediate during the nucleation step is clearly observed with a rotating ring-disk electrode. Decrease in the anodic ring current due to the reduction of soluble species formed during the anodic crystallization of lead dioxide at disk is detected.