New organically modified clays have been obtained from sodium montmorillonite, using either a cationic polyelectrolyte (polyethylenimine) or a novel homemade bisphenol-A silane as modifiers. The modification processes have been carried out in different reaction media, in order to Study the effects on the properties of the modified clays of several reaction parameters, such as the pH of the polyethylenimine Solution or the nature of the solvent used in the silanization. The obtained clays were characterized using X-ray diffraction, thermogravimetric analysis, and FTIR spectroscopy. Clays modified with polyelectrolyte or silane show significant increases in the basal spacing. The properties of polyelectrolyte-modified clays depend on the pH of the treating solution. The increase in the basal spacing of polyelectrolyte-modified clays varies only slightly with the pH: however, this reaction parameter clearly determines the total amount of polyelectrolyte introduced in the clay. The properties and applications of silane-modified clays are strongly dependent on the presence of water in the reaction media used for the silanization. These results have been explained by considering that the reaction conditions determine the nature and the amount of material intercalated into the clay. (C) 2009 Elsevier Inc. All rights reserved.