First principle calculations were performed for the first time to study the electronic structure of LiGaTe2, LiInTe2, and LiInSe2 chalcogenides with a chalcopyrite structure. Peculiarities of chemical bonding are discussed and electron density and difference density maps are constructed for crystals and sublattices. Major information about chemical bonding in crystals is conveyed by the difference density. The chemical bond in chalcogenides is a donor-acceptor bond.