Polymer–silicate nanocomposites were synthesized with atom transfer radical polymerization (ATRP). An ATRP initiator, consisting of a quaternary ammonium salt moiety and an α‐phenyl chloroacetyl chloride moiety, were intercalated into the interlayer spacings of the layered silicate. Subsequent ATRP of styrene with CuCl/2,2′‐bipyridine (bipy) as the catalyst with the initiator‐modified silicate afforded homopolymers with predictable molecular weights and low polydispersities, both characteristics of living radical polymerization. The polystyrene nanocomposites contained both intercalated and exfoliated silicate structures. The prepared materials were characterized by XRD, SEM, TEM, FTIR, and 1H NMR techniques. Effect of silicate on thermal properties and glass transition temperature of polystyrene was investigated using thermogravimetric analysis and differential scanning calorimetric techniques. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers