ZnO nanoparticles were covalently wrapped by polystyrene (PS) through surface thiol-lactam initiated radical polymerization using the grafting from approach. The surface of ZnO nanoparticles was initially modified by 3-mercapto propyltrimethoxysilane to afford thiol functionalized ZnO nanoparticles (ZnO-SH). The controlled radical polymerization of styrene (St) was subsequently accomplished by using an initiating system of ZnO-SH and butyrolactam. FT-IR, XPS, XRD, TGA, DSC, TEM and DLS were employed to investigate the chemical structure, morphology, thermal properties, the size and size distribution of nanocomposites. The dispersibility of ZnO nanoparticles was observed to be significantly improved upon functionalization by PS brushes. The controlled nature of the surface initiated thiol-lactam aided polymerization of St from the ZnO nanoparticles surface was confirmed by GPC analysis.