Silicon-methoxide-containing modified clays were obtained through cationic exchange between the sodium clay and the ammonium cation of [3-(trimethoxysilyl)propyl]octadecyldimethylammonium chloride (Si18). The nanocomposites were prepared through bulk polymerization of styrene in which the Si18 clay was dispersed. The silicon-methoxide offers the possibility of reaction between the methoxide and a clay hydroxyl group to link together the cation and the clay. The nanocomposites were characterized by X-ray diffraction, transmission electron microscopy, and atomic force microscopy. Their thermal stability and flame retardancy were measured by thermogravimetric analysis (TGA) and cone calorimetry. Linkage between the silicon and the clay apparently occurs in the clay but is not likely to occur in the nanocomposite, perhaps because of the presence of the polystyrene spreading the distance between the reactive sites, which makes reaction more difficult. The results from TGA and cone calorimetry were similar to those obtained with other nanocomposites.