The degenerative transfer copolymerization of vinyl acetate with ethene and higher 1-alkenes, as well as their fluoro derivatives (RfCH=CH2), under mild conditions was carried out using AIBN as the initiator and ethyl iodoacetate as the control agent. The obtained random copolymers were fairly high in alkene content, with high molecular weights and relatively narrow polydispersities. The quasi-living nature of the copolymerization allowed the synthesis of a block terpolymer by sequential addition of two different I-alkene comonomers to a vinyl acetate copolymerization system. The fluorinated side chains of vinyl acetate/fluoro alkene copolymers segregate toward the air-side of thin films, resulting in advancing water contact angle as high as 114 degrees. (c) 2005 Wiley Periodicals, Inc.