Kaolinite is one of the most important industrial clay minerals, with a worldwide consumption in the millions of tons per year and applications in a wide range of industrial areas. Traditionally, its most important use has been in the paper and ceramic industries. New, innovative techniques are being developed that are based on intercalation and grafting of kaolinite’s unique dipolar layer structure. Such techniques are leading the way to the synthesis of kaolinite–polymer nanocomposites, including bionanocomposites that might have value-added properties benefiting industry and the health sciences.