Natural iron (hydr) oxides commonly encounters Al substitution for Fe, which alters the microstructure, surface characteristics and reactivity of iron (hydr) oxides, and affects the chemical speciation and fate of elements in the soil. In this paper, the research progress on Al substitution of iron (hydr) oxides was summarized by bibliometrics, the effects of Al substitution on the microstructure, surface charge and interfacial reaction of iron (hydr) oxides were reviewed, and the mechanism of how Al substitution affected the surface adsorption of iron (hydr) oxides was elucidated from the aspects of electrostatic interaction, specific surface area, the composition and density of surface sites, the affinity of Fe /Al sites and vacancy defects. On the above bases, we proposed that future research should focus on the construction of a quantitative relationship of Al-substituted amount-microstructure-reactivity, the analysis of the adsorption mechanism of different crystal faces on Al-substituted iron (hydr) oxides, and the transition of the research object and system to the real soil.