A new synthetic methodology is developed for preparing graft copolymers via RAFT polymerization method by the R group approach onto styrenic polymers. In this approach, latent sites of the styrenic polymer was brominated first and then converted into macro-RAFT agents with pyrazole and thio dodecyl as the Z groups. This was used to synthesize graft copolymer such as polystyrene-graft-polymethyl methacrylate (PS-g-PMMA), polystyrene-graft-poly(isobornyl acrylate), polystyrene-graft-poly[2-(acetoacetoxy)ethyl methacrylate] (PS-g-PAEMA), and poly(para-methoxystyrene)-graft-polystyrene (P(p-MS)-g-PS). The polymers are characterized by gel permeation chromatography, 1H NMR, IR, and atomic force microscopy (AFM). The morphology of PS-g-PMMA in THF was investigated using AFM and island-like features were noticed. The AFM studies of the PS-g-PAEMA graft copolymers revealed the formation of globules and ribbon-like morphological features. The PS-g-PAEMA graft copolymers form complex with Fe(III) in dimethylformamide and the AFM studies suggest the formation of globular superstructures. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012