Polymer chains of PMMA were grown from nano titania (n-TiO2) spherical surfaces by the Reversible Addition Fragmentation Chain Transfer Polymerization process (RAFT) using the green solvent, supercritical carbon dioxide (scCO(2)). The RAFT agent (1), 4-cyano-4-(dodecylsulfanylthiocarbonylsulfanyl) pentanoic acid, with an available carboxyl group was first coordinated to the n-TiO2 surface, with the S=C(SC12H25) moiety subsequently used for RAFT polymerization of MMA to form the n-TiO2/PMMA nanocomposites. The livingness of polymerization was verified using GPC, while the morphology of the nanocomposites was studied using thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and dynamic light scattering (DLS). The rate of polymerization and molecular weights at different pressures in scCO(2) and in non-pressurized and pressurized organic solvent (THF) were compared, showing that increased CO2 pressure provided a higher rate of polymerization and longer chain lengths indicating the utility of this approach. (C) 2010 Elsevier Ltd. All rights reserved.