AbstractThe form of the NMR spectra obtained from liquid crystalline samples is discussed. It is shown how orientational order parameters can be derived from quadrupolar splittings and dipolar couplings, and their use in investigating possible forms for potentials of mean torque is illustrated for rigid solute molecules. For non‐rigid molecules, the observed partially‐averaged quadrupolar and dipolar couplings depend upon the nature of the internal rotations about bonds, as well as on the orientational order; it is shown how both of these factors can be investigated by NMR for both mesogenic molecules and for non‐rigid solutes. Finally, it is shown how deuterium NMR is being used to study field‐induced orientational order in the isotropic phase of mesogenic molecules.