Novel, well-defined fluorinated polystyrene was synthesized for the first time via the controlled radical polymerization of styrene through a relatively simple process and was characterized with H-1 NMR, F-19 NMR, and gel permeation chromatography. The surface properties of polystyrene and poly(acrylonitrile-co-butadiene-co-styrene) films were modified with the obtained polymers. X-ray photoelectron spectroscopy measurements of the air-side surface composition of the modified poly(acrylonitrile-co-butadiene-co-styrene) films showed that fluorine enriched the outermost surface, resulting in fantastic surface properties that came close to those of poly(tetrafluoroethylene). (c) 2006 Wiley Periodicals, Inc.