A series of well-defined binary hydrophilic-fluorophilic diblock copolymers were synthesized by successive atom transfer radical polymerization (ATRP) of methoxylmethyl acrylate (MOMA) and 4-(4'-p-tolyloxyperfluorocyclobutoxy)benzyl methacrylate (TPFCBBMA) followed by the acidic selective hydrolysis of the hydrophobic poly(methoxymethyl acrylate) (PMOMA) segment into the hydrophilic poly (acrylic acid) (PAA) segment. ATRP of MOMA was initiated by 2-MBP at 50 degrees C in bulk to give two different PMOMA homopolymers with narrow molecular weight distributions (M-w/M-n <= 1.15). PMOMA-b-PTPFCBBMA well-defined diblock copolymers were synthesized by ATRP of TPFCBBMA at 90 degrees C in anisole using Br-end-functionalized PMOMA homopolymer as macroinitiator and CuBr/PMDETA as catalytic system. The final PAA-b-PTPFCBBMA amphiphilic diblock copolymers were obtained via the selective hydrolysis of PMOMA block in dilute HCl without affecting PTPFCBBMA block. The critical micelle concentrations (cmc) of PAA-b-PTPFCBBMA amphiphilic copolymers in aqueous media were determined by fluorescence spectroscopy using pyrene as probe and these diblock copolymers showed different micellar morphologies with the changing of the composition. (C) 2010 Elsevier Ltd. All rights reserved.