Different behavior on the formation of soluble intermediate was observed depending on the substrate employed during the nucleation of lead dioxide from plumbous ion using a rotating ring-disk electrode. It was found that no soluble intermediate was formed at glassy carbon electrode, while the presence of soluble intermediate could be detected at platinum substrate. From the different anodic behavior of two substrates, the formation of a probable Pb(Ⅲ) soluble intermediate was suggested. A most probable nucleation mechanism at the platinum substrate involving a second order chemical reaction was derived on the basis