A unique feature of liquid crystals is a high degree of molecular mobility combined with orientational and positional order. Solid-state NMR contributes to fundamental understanding of diverse molecular organizations and complex dynamic processes in these exciting materials. The focus of this chapter is on the development and application of advanced solid-state NMR methodologies for liquid crystal studies, with emphasis on techniques for measuring anisotropic spin couplings. The discussion centers on applications of separated dipolar local field NMR spectroscopy, which is used in an increasing number of directions in studies of novel liquid-crystalline materials for emerging technological applications.