Nanocomposites based on poly(vinylidene fluoride) were prepared with montmorillonite by solution blending. The samples were characterized by small angle X-ray scattering, wide angle X-ray diffraction, Fourier transform infrared spectroscopy, and differential scanning calorimetry. Different crystallization conditions, that is, evaporation of the solvent and coprecipitation with two different antisolvents, H2O or supercritical CO2 (ScCO2), were tested and their influence on the resulting structure and morphology of the samples were studied. Coprecipitation with ScCO2 induced an ordinate crystalline framework and an intercalated morphology of clay, with a consequent large improvement in modulus. (c) 2008 Wiley Periodicals, fnc.