Enantiospecific recognition of chiral molecules plays an important role in nature as the basis of the interaction of chiral bioactive compounds with the chiral target structures. In separation sciences, such as chromatographic and capillary electromigration techniques, the formation of transient diastereomeric complexes between chiral analytes and chiral selectors in thermodynamic equilibria mediated via various intermolecular interactions is the basis for chiral separations. Because of the large structural variety of chiral selectors, different structural features contribute to the overall chiral recognition process. This introductory chapter briefly summarizes the present understanding of the structural enantioselective recognition processes for the types of chiral selectors most often applied.