This article describes the synthesis of bifunctional block copolymers (BCPs) of type 4 bearing orthogonally reactive backbone substituents such as 1,1,1,3,3,3-hexafluoroisopropoxycarbonyl groups as active esters and -hydroxyalkylphenylketones (2-hydroxy-2-methyl-1-phenylpropan-1-one) as additional photoactive moieties via reversible addition fragmentation chain transfer (RAFT) polymerization. As monomers 1,1,1,3,3,3-hexafluoroisopropyl acrylate (HFIPA) and 2-hydroxy-2-methyl-1-(4-vinyl)phenylpropan-1-one (HAK) are used. Controlled radical polymerization provides BCPs p(HFIPA)-b-p(HAK) with molecular weights (M-n) ranging from 15,000 to 37,000 g mol(-1) and low molecular weight distributions (PDI=1.2-1.4). The incorporated HFIPA and HAK moieties are used for sequential chemoselective postmodification of 4. The photoactive block of 4 can be functionalized through a nitroxide photoclick trapping reaction in the presence of functionalized nitroxides and the active ester moieties of the p(HFIPA)-block are readily thermally amidated using various amines. Chemically modified polymers are characterized by NMR, FTIR, and GPC methods which reveal a high degree of postfunctionalization, typically >95% for both orthogonal processes. The chemically modified polymers feature a narrow molecular weight distribution. The process is successfully applied to the synthesis of a small polymer library and also to the preparation of homo and block polynitroxides using 4-amino-TEMPO as amine component in the transamidation reaction. The polynitroxides obtained are characterized by cyclic voltammetry, FTIR, and UV-vis spectroscopy. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 52, 258-266