Well-defined homopolymer of 2,3,5,6-tetrafluorophenyl methacrylate (TFPM) was successfully synthesized via atom transfer radical polymerization (ATRP) technique. Controlled polymerization was achieved with the addition of CuBr2 as deactivator, which decreased the reaction rate and minimized the premature termination. The controlled/" living" polymerization behavior was supported by kinetic studies and the full chain extension for block copolymerization with 2-(dimethylamino) ethyl methacrylate (DMAEMA). Poly(TFPM) is an useful precursor for poly(methacrylamides) library syntheses. The active ester groups reacted with a variety of amines to produce a range of well-defined poly(methacrylamides), some of which would have been difficult to obtain by direct polymerizations of the methacrylamide monomers. Complete conversion to poly(methacrylamide) was achieved with unhindered primary amines. Substitution reactions with aromatic amines such as aniline did not occur under normal reaction conditions. (c) 2008 Elsevier Ltd. All rights reserved.