Fundamental problems related to aminoalcohols intercalating on kaolinite were investigated by using density functional theory method. This study examines the adsorption modes of diethanolamine and triethanolamine on kaolinite, the role of hydrogen bonds and van der Waals (vdW) forces between aminoalcohols and interlayer of kaolinite, and the change of molecular orbital occupancies of functionalized kaolinite. Results show that functionalized kaolinite is physically intercalated and covalently grafted by aminoalcohols. Non-covalent interaction analysis provides a visualized description that intercalated aminoalcohols form strong hydrogen bonds with Al octahedral sheet, and the interaction between aminoalcohols and Si tetrahedral sheet is mainly attributed to weak vdW force. The analysis of molecular orbital occupancies for kaolinite complex showed that the functionalized kaolinite has strong chemical reactivity as electron donors on the sites of grafted or intercalated aminoalcohols for further chemical reaction with other materials. (C) 2015 Elsevier B.V. All rights reserved.