Novel hybrids of poly(sodium acrylate) and natural and treated hectorites have been synthesized and characterized by X-ray diffraction, transmission electron microscopy analysis, and FTIR analysis. The thermal stability of these materials was studied. The swelling kinetics obey a Voigt-based equation. The experimental equilibrium water absorbency varies with the clay content and shows a minimum. All the hybrids showed excellent reswelling capability. Water desorption studies demonstrated the existence of ‘free water’ and ‘bound water’ within the polymeric matrix.