The present study determined the mineralogy and thermal properties of kaolin from Acoculco (Puebla), at the eastern Trans-Mexican Volcanic Belt and compared it with the nearby deposits of Agua Blanca (Hidalgo) and Huayacocotla (Veracruz). The mineralogy of the kaolins was determined by X-ray diffraction, infrared spectroscopy and scanning electron microscopy. Thermal behaviour was studied by differential thermal analysis, dilatometry and hot-stage microscopy. The Acoculco deposit is composed mainly of kaolinite and SiO2 minerals. In the case of Agua Blanca and Huayacocotla, alunite is abundant in places and minor anatase is also present locally. The Acoculco kaolins are Fe-poor and relatively rich in some potentially toxic elements (Zr, Sb, Pb). They undergo a relatively small amount of shrinkage (∼3–4 vol.%), during firing at 20–1300°C and cooling down to 20°C, except when >10 wt.% alunite is present. These kaolins are a suitable raw material for the ceramics industry. Other applications (pharmaceuticals, cosmetics) would require an enrichment process to eliminate impurities such as Fe oxides.