Langmuir and Langmuir-Blodgett (LB) films of novel rigid Schiff base amphiphiles with different polar groups on aromatic rings have been studied at air/water interfaces and on solid substrates. The local surface potentials for the different substituents on the aromatic groups of the amphiphiles are correlated to the surface energy of LB films on solid substrates. Their contributions are probed on high-surface-energy (hsfe) quartz and hydrophobically modified low-surface-energy (Isfe) quartz. Using theoretical estimates, the long-range effects of the substituents of the polar groups on the alkyl chains have been studied from charge on the carbon and hydrogen atoms of the alkyl tails. The calculations indicate that a substituted carbon atom has a charge that is directly dependent on the nature of the atoms to which it is attached rather than on the charges of any other atoms of the substituents. This work shows that the polar substituents on the head group clearly influence the distal methylene groups of the tail. Thus, any treatment, either theoretical or experimental, of these films in contact with solid substrates should include the local relative permitivities of the polar moieties, which seem to play an important role in determining macroscopic properties such as surface energy. (C) 2004 Elsevier Inc. All rights reserved.