The structures of 8,8′-bis(3-phenylthioureidomethyl)-2,2′-binaphthalene (1), 8,8′-bis(3-butylthioureidomethyl)-2,2′-binaphthalene (2) and their complexes with anionic guests such as carboxylate ions (acetate, oxalate, malonate, succinate, glutarate, adipate, pimelate, suberate, and azelate), inorganic oxygen-containing anions (nitrate, sulfate, bicarbonate, hydrogen phosphate, and dihydrogen phosphate), and halide ions (fluoride, chloride, and bromide) were obtained using the ONIOM approach. The binding abilities of receptors 1 and 2 to anionic species in terms of binding energy, thermodynamic properties, and selectivity coefficient were obtained at the ONIOM(B3LYP/6-31G(d):AM1) and BSSE-corrected B3LYP/6-31G(d)//ONIOM(B3LYP/6-31G(d):AM1) levels of theory. The multipoint hydrogen bonding between receptors (either the receptor 1 or 2) and anionic guests were found. The hydrogen phosphate is the most preferable ion to bind with either the receptor 1 or 2. © Springer Science+Business Media, LLC 2009.