In this article, the synthesis and the functionalization of well-defined, narrow polydispersity (polydispersity index < 1.2) star polymers via reversible addition-fragmentation chain transfer polymerization is detailed. In this arm first approach, the initial synthesis of a poly(pentafluorophenyl acrylate) polymer, and subsequent, cross-linking using bis-acrylamide to prepare star polymers, has been achieved by reversible addition fragmentation chain transfer polymerization. These star polymers were functionalized using a variety of amino functional groups via nucleophilic substitution of pentafluorophenyl activated ester to yield star polymers with predesigned chemical functionality. This approach has allowed the synthesis of star glycopolymer using a very simple approach. Finally, the core of the stars was modified via thiolene click chemistry reaction using fluorescein-o-acrylate and DyLigh 633 Maleimide. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 5245-5256, 2011