Poly(N-vinylcarbazole) covalently grafted zinc oxide nanoparticles (ZnO-g-PNVC) were synthesized with a simple route using surface initiated reversible addition-fragmentation chain transfer (RAFT) polymerization. Initially, the surface of ZnO nanoparticles was modified by the condensation reaction of 3-chloropropyltrimethoxysilane, and it was subsequently reacted with potassium xanthogenate to produce ZnO nanoparticles having RAFT functionality (ZnO-RAFT). The controlled radical polymerization of N-vinylcarbazole in the presence of ZnO-RAFT afforded ZnO-g-PNVC composites. FT-IR, EDX, XRD, and SEM analyses demonstrated the grafting of PNVC onto ZnO nanoparticles. Thermal stability of ZnO-g-PNVC composites was revealed by TGA analysis. UV-Vis absorption and photoluminescence results suggested ZnO-g-PNVC composites as a potential material in optical application.