This work analyzes the effects of ultrafine aluminum (Al) grains on the anodizing coating reaction and anticorrosion performance of anodized industrial pure Al. Equal-channel angular pressing (ECAP) was applied to cast pure Al continuously for 16 passes at room temperature, and its average grain size was dramatically refined to about 1.5 μm. The ultrafine-grain (UFG) pure Al was further anodized with a cast sample via a parallel anodizing circuit at a constant total input current. Benefited by the higher volume fraction of grain boundaries and higher internal energy of the UFG substrate, the anodizing process of the ECAP-processed pure Al was significantly accelerated, showing a more intense initial anodizing reaction, a faster initial coating thickening, and much earlier porous-layer formation compared to the cast sample. As the anodizing reaction continued, the newly formed thicker coating of the ECAP-coated sample significantly hindered the diffusion process, weakening the thermodynamic advantage and decreasing the anodizing current of the ECAP-processed sample. During the entire anodizing duration, the ECAP-processed pure Al experienced gradually decreased anodizing current, while the cast sample experienced increased anodizing current. Because of the more total reaction, the ECAP-coated sample always maintained a relatively thicker coating and better anticorrosion performance during the entire anodizing duration.