Fourteen anions were selected to investigate their adsorption capacities and affinities to unwashed and washed hexadecyl pyridinium (HDPy)-modified montmorillonite (HDPy/Mt). Correlations between adsorption characteristics and anionic properties including radius and hydration energy were determined. With the exception of IO3-, H2AsO4-, and CrO42-, monovalent anions showed higher adsorption capacities and affinities to unwashed or washed HDPy/Mt than divalent anions, because the latter possess higher hydration energies. Unwashed HDPy/Mt demonstrated higher selectivity toward poorly hydrated monovalent anions because it presented a more hydrophobic environment, whereas strongly hydrated divalent anions more readily intercalate into the less hydrophobic washed HDPy/Mt. Hydration of the counter ion (Cl-) is the driving force for anion adsorption on HDPy/Mt. Higher energy consumption required to dehydrate divalent anions accounts for their lower affinity. Selectivity of HDPy/Mt to anions depends not only on anion size in different phases (from r(1) in aqueous solution to r(2) in the organic solvent-like HDPy/Mt), but also the dielectric constant of HDPy/Mt (epsilon(2)) after HDPy release. (C) 2016 Elsevier B.V. All rights reserved.