The significance of the Liftshitz/van der Waals, Lewis-acid, and Lewis-base contributors to the total surface energy of a material is discussed in terms of the molecular design features and surface organization phenomena characterizing film structures prepared from four homologous series of polymeric compounds, namely the poly(methylpropenoxyperfluoroalkylsiloxane)s the poly(methylpropenoxyalkylsiloxane)s, the poly(perfluoroalkylacrylate)s, and the poly(alkylacrylate)s.