The relationship between kaolinite structure and the temperature of thermal transformation of phase was discussed in this paper through grinding and heating treatment. The results show that the structure of kaolinite is destroyed rapidly with increasing mechanical grinding time, and the kaolinite structure collapses completely after 1 h grinding. The temperature of thermal transformation of phase decreases with the destruction of kaolinite structure. This result has a great significance for the utilization of kaolinite associated with coal measures in China.