Reversible addition-fragmentation chain transfer (RAFT) polymerization enables the synthesis of controlled architectures for a wide-variety of polymers with defined end and pendant functionalities using mild conditions. A simple synthetic route for the preparation of polystyrene (PS)/ZnO nanocomposite with well-defined structure is demonstrated. ZnO nanoparticles were synthesized by homogeneous precipitation. To reduce the aggregation among ZnO nanoparticles, an effective surface modification method was proposed by grafting polystyrene onto the ZnO particles. The surface of ZnO nanoparticles was firstly treated with a 4-cyano-4-[(4-methoxyphenyl carbon thiol) solfanylvaleric acid] coupling RAFT agent in the presence of THF as a solvent at 65 degrees C. A carboxylic group in raft agent attached to ZnO nanoparticles by the esterification reaction with the hydroxyl groups on the ZnO particle surface. Then, RAFT polymerization of styrene was subsequently conducted to graft PS onto the exterior surface of ZnO nanoparticles by new RAFT agent 4-cyano-4-[(4-methoxyphenyl carbon thiol) solfanylvaleric acid]. The obtained nanocomposite was characterized by Fourier transform infrared spectroscopy (FT-IR), thermo gravimetric (TGA), transmission electron microscopy (TEM), and X-ray powder diffraction (XRD). (C) 2015 Society of Plastics Engineers