Aromatic monomers with different fluorine concentrations and structural distribution patterns were synthesized. A series of copolymers based on methyl methacrylate, acrylate, and perfluorooctylalkyl acrylate were prepared by emulsion polymerization and were subsequently used as functional coatings to prepare water- and oil-repellent cotton fabrics. The composition and structure of the outmost layer of the treated cotton surface were analyzed. A strong surface segregation of fluorinated segments was found for the treated samples, as shown by X-ray photoelectron spectroscopy analysis. The basis for an in-depth appreciation of the relationship between the molecular structure of the monomers and the properties of corresponding copolymer-treated materials was provided (especially with regarding to their hydrophobic and oleophobic properties). The wetting characteristics of the fluorinated copolymers were found to be dependent on the density (number of side chains per constitutional repeat unit) and regularity of the fluorinated side chains. (c) 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4410-4418, 2013