The most stable structures and electronic properties of different Li/Al layered double hydroxides models (i.e., Li/Al-X, X = F-, Cl-, Br-, OH-, NO3-, CO32-, SO42-) and their hydrates, the adsorption of CO2 on Li/Al-X (X= Cl-, NO3-, CO32-) were ascertained by means of density functional theory. Results revealed that the planes of NO3- and CO32- are parallel with the layers in dehydrated state, although the plane of NO3- becomes vertical with the layers upon the introduction of water molecules. Electronic density analysis suggested that SO42- and CO32- significantly strengthens the reducibility of the Li/Al layered double hydroxides. The distribution of the frontier orbitals indicated the high reactivity of the anions and hydroxyl groups of the layers. The orders of the predicted stability are F- > Cl- >Br- >NO3- for the monovalent anions and SO42- > CO32- for the divalent anions. The calculated adsorption energies of CO2 in Li/Al-X (X= Cl-, NO3-, CO32-) supported the experimental observation that Li/Al-CO3 exhibits higher CO2 capture capacity than Li/Al-NO3 and Li/Al-Cl. Non-covalent interaction analysis indicated that the interactions among mineral surfaces, anions, water and CO2 are dominated by H-bonds, electrostatic interactions, and van der Waals forces. In addition, radial distribution functions were applied to provide insight for the interaction of water or CO2 with carbonate ion and hydroxyl layers. (C) 2017 Elsevier B.V. All rights reserved.