An overview is presented of modern NMR techniques and a variety of experimental and theoretical tools employed in the study of solutes dissolved in liquid crystals. The NMR techniques involve multiple quantum and spectral subtraction methods. In addition, various experimental and theoretical tools are discussed, including: the theoretical background of observed order parameters; the use of 'magic mixtures' to separate orientational contributions; the reorientation-vibration interaction; the use of model calculations based on size and shape of the various solutes; and the use of computer simulations. Applications to the benchmark probe molecules hydrogen, methane, ethane, and butane and their isotopomers are treated. © 2005 Elsevier Inc. All rights reserved.