Abstract: The i.r. spectra of interlamellar kaolinite complexes with formamide, N-methylformamide and dimethylformamide have been examined. The spectra show that the amides hydrogen-bond, through the C=O group of the amide to the inner surface kaolinite hydroxyls and decrease the intensity of the kaolinite ν(OH) bands. Hydrogen-bonded kaolinite hydroxyl bands appear at lower frequencies and these have been correlated to the original kaolinite ν(OH) bands. Other kaolinite bands in the complexes show smaller perturbations of the kaolinite vibrations. Each amide hydrogen-bonds to different groups of hydroxyls. Formamide hydrogen-bonds to the 3690 and 3664 cm−1 hydroxyls, N-methylformamide to the 3690 and 3648 cm−1 hydroxyls. The interpretation for the dimethylformamide complex is less clear. The ν(NH) frequencies of formamide and N-methylformamide in the complexes are intermediate between that in dilute non-polar solution and in the liquid. This could arise from either or both a degree of intermolecular association of the amide when between the kaolinite lamellae, or to weak N—H … O hydrogen bonds to the tetrahedral oxygen sheet of the lamellae.