The molecular motion in the synthetic bilayer membranes formed from a series of single-chain ammonium amphiphiles with a rigid Schiff base segment, the diphenylazomethine chromophore, has been investigated via the use of H-1 NMR spectroscopy. The changes in chemical shift of the azomethine protons suggest the effect of conformation and aggregation variation during the bilayer formation process, which confirms the concept of conformation control of the supramolecular systems containing a nonplanar chromophore.