AbstractA general review of applications of selective excitation techniques is provided. The different methods for suppression of solvent signal are summarized. The theoretical basis of selective population inversion and selective polarization transfer is considered and applications are treated. Direct observation of chemical‐exchange processes is discussed for both the two‐site and the multi‐site system. Finally, the potential of selective excitation techniques for extracting structural and dynamic information from single‐ and double‐selective relaxation rates is addressed, with particular emphasis given to NMR studies of small ligands bound to macro