A kaolinite-poly (vinylpyrrolidone) intercalation compound has been prepared by the intercalation of an N-vinyl-2-pyrrolidone monomer (VP) and subsequent heat treatment. The intercalation of VP was achieved by treating a kaolinite-ammonium acetate intercalation compound with a VP aqueous solution. The basal spacing decreased from 14.2 to 12.6A, and infra-red spectroscopy (IR) and solid-state 13C nuclear magnetic resonance with cross polarization and magic angle spinning techniques (13C CP/MAS NMR) showed the displacement of ammonium acetate by VP. When the kaolinite-VP intercalation compound was heated at 200°C for 1h, the basal spacing did not vary. The IR and 13C CP/MAS NMR spectra showed the disappearance of vinyl groups and became similar to those of poly (vinylpyrrolidone) (PVP). These results clearly indicate the polymerization of VP between the layers of kaolinite.