A viscous reverse hexagonal surfactant mesophase containing bis(2-ethylhexyl) sodium sulfosuccinate (AOT) and a-phosphatidylcholine (lecithin), with comparable volume fractions of isooctane and water, was characterized by Fourier transform P-31 and H-1 NMR spectroscopy. Shear alignment was reflected through both P-31 NMR and 1H NMR spectra. A complicated P-31 spectrum was observed as a result of superposition of chemical shifts according to the distribution of crystalline domains prior to shear. The initially disordered samples with polydomain structures become macroscopically aligned after Couette shear. P-31 NMR chemical shift anisotropy characteristics are used to elucidate orientation of the hexagonal phase. Interestingly, H-1 NMR spectra exhibit spectral changes upon shear alignment closely corresponding with that of P-31 NMR spectra. These observations complement the findings of mesophase alignment obtained using SANS and imply that P-31 and H-1 NMR spectroscopy can be used as probes to define microstructure and monitor orientation changes in this binary surfactant system. This is especially beneficial if these mesophases are used as templates for materials synthesis.