We report a simple and robust method to self-assemble porous anodic aluminum oxide membranes with serrated nanochannels by anodizing in phosphoric acid solution. Due to high field conduction and anionic incorporation, an increase of anodizing voltage leads to an increase of the impurity levels and also the field strength across barrier layer. On the basis of both experiment and simulation results, the initiation and formation of serrated channels are attributed to the evolution of oxygen gas bubbles followed by plastic deformation in the oxide film. Alternating anodization in oxalic and phosphoric acids is applied to construct multilayered membranes with smooth and serrated channels, demonstrating a unique way to design and construct a three-dimensional hierarchical system with controllable morphology and composition.