The significance of the Liftshitz/van der Waals, Lewis-acid, and Lewis-base contributors to the total surface energy of an homologous series of poly(di-1H,1H,2H,2H-perfluoroalkylitaconate)s is discussed in terms of the molecular design features and surface organisation phenomena characterising these, comb-like, polymers. Comparison of the characteristics specific to films prepared from this class of materials with those of the previously-studied homologous series of poly(perfluoroalkylacrylate)s, poly(perfluoroalkylmethacrylate)s and poly(methylpropenoxyalkyl siloxane)s suggests that, of the molecular design requirements for low-surface-energy polymers, an increase in the packing density of pendent side-chains has little effect on the contributors to surface energy but an adverse effect on the roughness of the film.