Hydration treatment of aluminum in hot water is important for its corrosion protection, and also this treatment is a crucial pretreatment in forming dielectric crystalline alumina films on the aluminum anode in aluminum electrolytic capacitors. In this study, a two-layer hydrated film formed on high purity aluminum by hot water treatment was examined using a combination of glow discharge (GD) sputtering and Raman spectroscopy. In addition, the anion penetration behavior through the hydrated alumina layer during anodizing aluminum in several electrolytes was investigated. The results indicate that the outer layer, with a nanosheet-like morphology, consists of a crystalline pseudo-boehmite phase, whereas the relatively compact inner layer is amorphous or poorly crystalline. The inner amorphous layer plays a crucial role in the incorporation of the anions, which is found for the first time. When hydrated aluminum is anodized in phosphate, silicate, and tungstate electrolytes, the inner hydrated alumina layer impedes the penetration of these electrolyte anion species. In contrast, boron species readily penetrate the hydrated alumina layer into the barrier layer formed by anodization in boric acid. This anion-specific incorporation behavior is discussed in terms of ion-selective permeation in the amorphous hydrated alumina layer.