Radioactive caesium pollution resulting from Fukushima Dai-ichi and Chernobyl nuclear plant accidents involves strong interactions between Cs+ and clays, especially vermiculite-type minerals. In acidic soil environments, such as in Fukushima area, vermiculite is subjected to weathering processes, resulting in aluminization. The crystal structure of aluminized clays and its implications for Cs+ mobility in soils remain poorly understood due to the mixture of these minerals with other clays and organic matter. We performed acidic weathering of a vermiculite to mimic the aluminization process in soils. Combination of structure analysis and Cs+ extractability measurements show that the increase of aluminization is accompanied by an increase in Cs+ mobility. Crystal structure model for aluminized vermiculite is based on the interstratification of unaltered vermiculite layers and aluminized layers within the same particle. Cs+ in vermiculite layers is poorly mobile, while the extractability of Cs+ is greatly enhanced in aluminized layers. The overall reactivity of the weathered clay (cation exchange capacity, Cs+ mobility) is then governed by the relative abundance of the two types of layers. The proposed layer model for aluminized vermiculite with two coexisting populations of caesium is of prime importance for predicting the fate of caesium in contaminated soil environments.