Poly(4-vinylpyridine) was covalently wrapped onto ZnO nanoparticles through surface initiated Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization upon grafting from protocol. The surface of ZnO nanoparticles was initially modified by the coupling reaction with silane leading to trithiocarbonate functionalized ZnO nanoparticles (ZnO-RAFT). The controlled radical polymerization of 4-vinylpyridine in the presence of the ZnO-RAFT afforded PVP-g-ZnO nanocomposites. FT-IR, EDX, XRD and XPS analyses demonstrated the grafting of PVP on the surface of ZnO nanoparticles, while thermal stability of PVP-g-ZnO nanocomposites was confirmed by TGA analysis. The TEM and SEM images suggested that ZnO nanoparticles were embedded in the polymer, and the dispersibility of the nanocomposites was improved in an organic solvent dramatically.