Intercalation is a significant control method to achieve high value of kaolinite. It is important to investigate the intercalation process of kaolinite for the perspective of atomic and molecular scale and energy. This review represented recent work on theoretical calculation of intercalated kaolinite, i.e., the intercalation of inorganic and organic small molecules as well as organic macromolecular. In addition, the future development direction of intercalation of kaolinite was also prospected.