Novel amphiphilic fluorinated ABC-type triblock copolymers composed of hydrophilic poly(ethylene oxide) monomethyl ether (MeOPEO), hydrophobic polystyrene (PSt), and hydrophobic/lipophobic poly(perfluorohexylethyl acrylate) (PFHEA) were synthesized by atom transfer radical polymerization (ATRP) using N,N,N',N '',N ''-pentamethyldiethylenetriamine (PMDETA)/CuBr as a catalyst system. The bromide-terminated diblock copolymers poly(ethylene oxide)-block-polystyrene (MeOPEO-b-PSt-Br) were prepared by the ATRP of styrene initiated with the macroinitiator MeOPEO-Br, which was obtained by the esterification of poly(ethylene oxide) monomethyl ether (MeOPEO) with 2-bromoisobutyryl bromide. A fluorinated block of poly(perfluorohexylethyl acrylate) (PFHEA) was then introduced into the diblock copolymer by a second ATRP process to synthesize a novel ABC-type triblock copolymer, poly(ethylene oxide)-block-polystyrene-block-poly(perfluorohexylethyl acrylate) (MeOPEO-b-PSt-b-PFHEA). These block copolymers were characterized by means of proton nu-clear magnetic resonance (H-1 NMR) and gel permeation chromatography (GPC). Water contact angle measurements revealed that the polymeric coating of the triblock copolymer (MeOPEO-b-PSt-b-PFHEA) shows more hydrophobic than that of the corresponding diblock copolymer (MeOPEO-b-PSt). Bovine serum albumin (BSA) was used as a model protein to evaluate the protein adsorption property and the triblock copolymer coating posseses excellent protein-resistant character prior to the corresponding diblock copolymer and polydimethylsiloxane. These amphiphilic fluoropolymers can expect to have potential applications for antifouling coatings and antifouling membranes. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem49: 1528-1534, 2011