The application and growth mechanism of anodic TiO 2 nanotubes have been a hot topic in the last ten years, but the formation mechanism of anodic ZrO 2 nanotubes has rarely been studied. In one-step constant voltage anodization of Al and Ti, the typical current-time curve has three stages. Moreover, the current-time curves of the three stages can last for 10 min or even 10 hours, resulting in a single layer of nanotubes with the same diameter due to the constant voltage in one-step anodization. However, in this paper, it was found for the first time that the three stages of the current-time curve appeared twice in succession during one-step constant voltage anodization of Zr for only 900 seconds, and bilayer nanotubes with increased diameter were obtained. This six-stage current-time curve cannot be explained by classical field-assisted dissolution and field-assisted flow or stress-driven mechanisms. Here, the formation mechanism and growth kinetics of bilayer ZrO 2 nanotubes have been clarified rationally by the theories of ionic current, electronic current and oxygen bubble mold. The interesting results presented in this paper are of great significance for revealing the anodizing process of various metals and the formation mechanism of porous structures.