A series of polyacrylate monomers with F-alkylalkyl [F(CF2)(n)(CH2)(n')] side groups were prepared by free-radical polymerization. The effect of the chemical structure on the surface properties of poly(ethylene terephthalate)s was evaluated by variations in the relative length of the fluorocarbon and hydrocarbon units in the side group. The resulting polymers were quite surface-active in the solid state. The surface and bulk organization was investigated by X-ray photoelectron spectroscopy analysis. A strong correlation between the bulk organization and surface properties of the polymers was established. The outmost layer, formed from trifluoromethyl groups and some ester functions, suggests that the side chain is arranged irregularly in the polymer-air interface. The length of the lateral chain governs this organization: long fluorinated chains and short hydrocarbon spacers are essential elements of the molecular design for such low-surface-energy materials. (c) 2005 Wiley Periodicals, Inc.