Polystyrene (PS)/clay nanocomposites were prepared with two different new intercalation organophilic clays, the phosphonium salt (APP) and the ammonium 4-(4-adamantylphenoxy)-1-butanamine (APB) salts, by emulsion polymerization technique. X-ray diffraction and transmission electron microscopy were performed to characterize the layered structures of APB- and APP-treated polymer-clay nanocomposites, and both resulted in exfoliated structures. Molecular weights of PS obtained from these nanocomposites are slightly lower than the virgin PS formed under similar polymerization conditions. Coefficient of thermal expansion showed approximately a 44-55% decrease for APB- and APP-intercalated clay nanocomposites relative to the pure PS. Both T-g and thermal decomposition temperature of the PS component in the nanocomposite are higher than the virgin PS, implying that the presence of clay is able to enhance thermal stabilities of the PS. (c) 2007 Wiley Periodicals, Inc.