The chemical composition of kaolin in coal measures of Jinyang, Mengxi and Xuena is SiO₂ and Al₂O₃ with low content of K, Na, Ca and Mg and relatively high content of Fe and Ti. The mineral composition is mainly kaolinite with minor boehmite, quartz and montmorillonite. The XRD and IR analytical results reveal that kaolinite in Jinyang and Mengxi exhibits a highly ordered structure with HI index being 1.19 and 1.23, while kaolin from Xuena shows dispersed and low symmetry diffraction peaks, with HI index being only 0.56. On such a basis, kaolin_dimethyl sulfoxide and kaolin_formide intercalation composite was prepared. The XRD patterns indicate that dimethyl sulfoxide and formide can insert into the inter layer of kaolinite and increase the interplanar spacing. Kaolin from Jinyang has the best intercalation ratio, kaolin from Xuena takes the second place, and kaolin from Mengxi is the worst.