Changes in the molecular structure of a highly ordered kaolinite, intercalated with urea and potassium acetate, have been studied using Raman microscopy. A new Raman band, attributed to the inner surface hydroxyl groups strongly hydrogen bound to the acetate, is observed at 3605 cm (super -1) for the potassium acetate intercalate with the consequential loss of intensity in the bands at 3652, 3670, 3684 and 3693 cm (super -1) . Remarkable changes in intensity of the Raman spectral bands of the low-frequency region of the kaolinite occurred upon intercalation. In particular, the 144 and 935 cm (super -1) bands increased by an order of magnitude and were found to be polarized. These spectroscopic changes provide evidence for the inner surface hydroxyl group-acetate bond being at an angle approaching 90 degrees to the 001 face. Decreases in intensity of the bands at 243, 271 and 336 cm (super -1) were observed. The urea intercalate shows additional Raman bands at 3387, 3408 and 3500 cm-1 which are attributed to N-H vibrations after formation of the urea-kaolinite complex. Changes in the spectra of the inserting molecules were also observed.