For the first time, a detailed study of the atom transfer radical polymerization of isobornyl acrylate (iBA) is reported. On the basis of these results, well-defined PiBA-containing block copolymers were synthesized, focussing on the preparation of amphiphilic poly(acrylic acid) (PAA) containing block copolymers. The precursor monomers 1-ethoxyethyl acrylate (EEA) as well as tert-butyl acrylate have been used to synthesize the PAA-segments of the PiBA-b-PAA block copolymers. Finally, the synthesis of "block-like" copolymers of PiBA and PEEA via a one-pot procedure was investigated. By optimizing the copper and ligand concentration, and choosing the appropriate solvent, a controlled polymerization behaviour was obtained in all cases, as evidenced by a detailed kinetic analysis, GPC, NMR, and MALDI-TOF data. Thermogravimetric analysis confirmed the quantitative transformation of the precursor polymer PEEA to the corresponding PAA-containing copolymers. (C) 2008 Wiley Periodicals, Inc.