Soap-free emulsion copolymerization of perfluoroalkyl acrylate (FA)/methyl methacrylate (MMA)/n-butyl acrylate (n-BA) was carried out in the presence of sodium 2-acrylamide-2-methyl propanesulfonate (AMPSNa) as a reactive surfactant and potassium persulfate (KPS) as an initiator. An analysis of the effects of concentration of AMPSNa, KPS, FA as well as polymerization temperature on the kinetic features (rate of polymerization) and colloidal characteristics (mean particle diameter, particle disperse index, particle numbers, and surface charge density) was followed. NMR, FTIR, AFM, and fluorine-selective electrode analysis were used to characterize the composition and morphology of the FA copolymers. Both AFM analysis and contact angle measurements strongly implied that the fluorinated segments migrated to the outmost surface and created films with lower surface energy. (c) 2007 Wiley Periodicals, Inc.