The significance of the Liftshitz/van der Waals, Lewis-acid, and Lewis-base contributors to the total surface energy of a homologous series of poly(perfluoroalkyl methacrylate)s is discussed in terms of the molecular design features and surface organization phenomena characterizing these polymeric compounds. The study suggests that, of the molecular design requirements for low-surface-energy polymers, a flexible backbone is not an essential feature.