A chemical route for the delamination of kaolinite in a polymeric matrix is reported in this work. The strategy that was used is based on mixing polyelectrolytes of opposite charges, an organic polyanion, polyacrylate, with an inorganic polycation resulting from the modification of the internal surfaces of kaolinite. The delamination was carried out by the reaction of sodium polyacrylate (PANa) with kaolinite whose internal aluminol surfaces were previously grafted with triethanolamine and subsequently quaternized with iodomethane (TOIM-K) to form an extended lamellar inorganic polycation. X-ray diffraction as well as scanning electron microscopy (SEM) confirmed the complete delamination of the kaolinite particles. 13C CP/MAS NMR showed the removal of the ammonium groups resulting from hydrolysis of the internal surfaces once exposed, and 29Si CP/MAS NMR spectra were in agreement with the retention of the 1:1 aluminosilicate kaolinite layers structures. From the thermogravimetry (TG) data, the respective percentages in mass of PA and kaolinite in the delaminated nanocomposite could be estimated to be 61% and 39%, respectively, in the conditions of the particular experiment. The procedure was repeated several times to show the reproducibility of the delamination. The interlayer functionalization of kaolinite was crucial for the success of the delamination procedure. SEM pictures show that some individual kaolinite platelets fold and form curved structures.