The design of a novel rare earth optical-functional hybrid material based on reversible addition-fragmentation chain transfer (RAFT) polymerization was detailed. The hydroxyl groups on the silica hollow sphere surface were converted into trithiocarbonate chain transfer agents (CTA), and were further used to mediate the RAFT polymerization of methyl methacrylate (MMA). Hollow sphere-g-poly(methyl methacrylate)-block-terbium (HS-g-PMMA-b-Tb) optical-functional hybrid materials were obtained by grafting the Tb complex to the end of the PMMA chains via RAFT polymerization. The samples were characterized by XPS, FT-IR, TGA and SEM respectively. The results indicated that the MMA had grafted from the surface of the hollow sphere successfully and the average diameter of the hollow spheres was about 1.1 mu m. The fluorescence properties of the HS-g-PMMA-b-Tb hybrid materials were also investigated. (C) 2009 Elsevier Ltd. All rights reserved.