Abstract: Sorption of aniline and its derivatives by montmorillonite substituted by cations of widely different acidity depends upon the polarizing power of the interlayer cations. Infra-red spectra indicate that the anilines are mostly bound to the interlayer cations through water molecules, except in Cs montmorillonite, where bonding to the oxygen surfaces of the alumino-silicate sheets seems to predominate. Anilines are weak bases, which compete with the oxygen surfaces for protons of acidic interlayer water. Consequently, the tendency of anilines to act as proton donors in the clay interlayers increases with the polarizing power of the exchangeable cation. The concept of ‘basic’ water is introduced to account for some of the features of the spectra of Cs montmorillonite treated with the organic ligands.