Pharmaceutical solids have generally been characterized as either threedimensional crystals or amorphous solids based on X-ray powder diffraction and modulated temperature differential scanning calorimetry. In contrast, fewer examples of thermotropic and lyotropic liquid crystals, or mesophases, appear in the pharmaceutical literature, and that literature teaches that the aforementioned analytical techniques should be complemented with polarized light microscopy and small-angle X-ray scattering in order to effectively identify potential liquid crystalline states. Lyotropic liquid crystals are induced by the presence of solvent, and have been extensively described elsewhere in the context of emulsion technology; however, other pharmaceutical examples are emerging. Thermotropic liquid crystals are induced by a change in temperature and are essentially free of solvent, where more pharmaceutical applications appear in the literature. In the present review the general structural characteristics that favor the formation of liquid crystalline mesophases are categorized by therapeutic target and molecular size, and the analytical means of their identification are presented.