The ordering parameters of selected Solutes from NMR spectroscopic measurements have been assessed in the thermotropic and amphotropic smectic liquid-crystalline phases of a wide structural range of phosphonium salts with three equivalent long n-alkyl chains, one shorter chain, and various anions. The nature liquids that convert the salts to amphotropic phases-alcohols and other small organic molecules-and their concentrations have been determined. These factors are correlated with the NMR-derived parameters in order to understand how the phases can be optimized to maximize information about the solutes. The various salts cover a range of liquid crystallinity from -40 to 100 degrees C. The phosphonium salts are easily aligned in the strong magnetic fields of the spectrometers. In several of the systems, a coexistence of isotropic and anisotropic phases is observed over a wide range of temperatures. The order parameters of the amphotropic liquid-crystalline phases vary from high to very low values, and some of the systems provide good spectral resolution for the solute molecules. Also, structural and orientational parameters of a model molecule, C-13-enriched acetonitrile, have been calculated in various systems in order to evaluate more precisely the applicability of the host systems for determining solute structures by NMR. The results, in toto, indicate that several of the phosphonium salts are very promising as hosts to determine solute structures.