Polystyrene-clay nanocomposite (PsCN) materials have been prepared by a free radical polymerization process. Montmorillonite (MMT), modified by two different organics, was investigated: one contains a short chain and three benzyl groups on the ammonium ion (DAETPB), while the other contains a long chain (HTAC). The organic modification determines the extent of exfoliation or intercalation of the materials. Exfoliation is more likely to occur using HTAC, as then the gallery of clay has been opened more due to the long chain structure. Exfoliation of MMT in polystyrene (PS) matrix was revealed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were employed to confirm the increased thermal stability of these PsCN materials. Dielectric properties of polystyrene-clay nanocomposites, in the form of film with clay loading from 1.0 to 5.0 wt %, were measured under frequencies of 100 Hzsimilar to1 MHz at 25similar to70degreesC. Decreased dielectric constant and low dielectric loss were observed for PsCN materials. Especially, the decrease of dielectric constant was found to be related to the extent of exfoliation of clay. It is recognized that the confinement effect of clay results in the suppression of the dielectric response of the nanocomposite materials at low frequency. (C) 2004 Wiley Periodicals, Inc.