We explored phase separation and self-assembly of perfluoroalkyl segments at the surface of polymer films obtained from latices of semifluorinated acrylate copolymers and the corresponding latex blends of nonfluorinated and semifluorinated polyacrylates. With laser-induced secondary mass spectrometry the fluorine distribution was measured after annealing above the minimum film-forming temperature of the polymers up to a depth of several micrometers. Depth profiles of a semifluorinated acrylate homopolymer and latex blends thereof with fluorine-free alkylacrylates with 25, 50, and 75 mol % semifluorinated acrylate as well as a copolymer comprised of alkyl acrylate and semifluorinated acrylate (50/50 mol %) were investigated. In the case of latex blends containing both semifluorinated polyacrylates and fluorine-free or low-fluorine polymers, self-assembly accounted for enrichment of the perfluoroalkyl segments at the surface. Coatings exhibiting low surface energy and having a substantially reduced total fluorine content were obtained. (C) 2003 Wiley Periodicals, Inc.