Abstract Since the first publication on this subject in 1963, NMR in liquid crystalline systems has been a wide and active field of research in many branches of chemistry, physics, biology, and materials science. Indeed, thanks to the wealth of exploitable nuclei and interactions, NMR spectroscopy has revealed a powerful means of probing structure and dynamics of molecules dissolved in liquid crystals. Moreover, NMR spectroscopy has been successfully employed to investigate properties of mesophases themselves, such as their molecular organization and orientational ordering, translational and rotational motions, and response to external stimuli such as temperature, pressure, and magnetic and electric fields. NMR spectroscopy of liquid crystals and of solutes dissolved in liquid crystals is described. The molecular structure and dynamic information that can be obtained from such studies is outlined.