The phase behavior of amphiphiles, e.g., lipids and surfactants, at low water content is of great interest for many technical and pharmaceutical applications. When put in contact with air having a moderate relative humidity. amphiphiles often exhibit coexistence between solid and liquid crystalline phases, making their complete characterization difficult. This study describes a (13)Csolid-state NMR technique for the investigation of amphiphile phase behavior in the water-poor regime. While the C-13 chemical shift is an indicator oft molecular conformation, the C-13 signal intensities obtained with the CP and INEPT polarization transfer schemes yield information on molecular dynamics. A theoretical analysis incorporating the effect or molecular segment reorientation, with the correlation time tau(c) and order parameter S. shows that INEPT is most efficient for mobile segments with tau(c) < 0.01 mu s and S < 0.05, while CP yields maximal signal for rigid segments with tau(c) > 10 mu s and/or S > 0.5 under typical solid-state NMR experimental conditions. For liquid crystalline phases, where tau(c) < 0.01 mu s and 0 < S < 0.3, the observed CP and IN EFT intensities serve as a gauge of S. The combination of information on molecular conformation and dynamics permits facile phase diagram determination for systems with solid crystalline, solid amorphous, anisotropic liquid crystalline, and isotropic liquid (crystalline) phases as demonstrated by experiments on a series of reference systems with known phase structure. Three solid phases (anhydrous crystal, dihydrate, gel), two anisotropic liquid crystalline phases (normal hexagonal, lamellar), and two isotropic liquid crystalline phases (micellar cubic, bicontinuous cubic) are identified in the temperature-composition phase diagram of the cetyltrimethylammonium succinate/water system. Replacing the succinate counterion with DNA prevents the formation of phases other than hexagonal and leads to a general increase of tau(c).