Polymericaly modified clays that contain an oligomeric poly (styrene-co-chloromethyl styrene) ammonium salt have been prepared and used to preparation of polystyrene (PS) nanocomposites. First, PS and poly(styrene-co-chloromethyl styrene) [P(St-co-CMSt)] were synthesized by nitroxide mediated living free radical polymerization (NMRP) by TEMPO iniferter .Then the copolymer was coupled with N, N-dimethyl hexadecyl amine to prepare polymeric modifier by anion exchange of chlorine group of chloromethyl styrene (CMSt) by quaternary amine. The synthesized polymeric modifier was mixed with nanoparticle of silica to change the property of clay surface from hydrophilic to hydrophobic via cation exchange of Na 1 with alkylammonium ions. For synthesizing of nanocomposites, we used polymericaly modified montmorillonite and PS that was synthesized by NMRP technique. Intercalated nanocomposites and in some cases, exfoliated or mixed intercalated/exfoliated nanocomposites of all of these polymers have been produced by solution blending method. The prepared materials were characterized by X-ray diffraction, Transmission electron microscopy, Fourier-transform infrared, 1 H nuclear magnetic resonance, and gel permeation chromatography techniques. Effect of layered silicates on thermal properties and glass transition temperature of PS was investigated using TGA and DSC techniques. POLYM.