The stereoselective recognition of chiral molecules is an important aspect in nature as the basis of the interaction of chiral bioactive compounds with their target structures. In separation sciences such as chromatographic and capillary electromigration techniques, the formation of transient diastereomeric complexes between chiral analytes and chiral selectors via hydrogen and halogen bonds , ionic, ion-dipole, dipole-dipole, van der Waals as well as π-π interactions is the basis for chiral separations . Spectroscopic techniques, especially nuclear magnetic resonance spectroscopy , as well as molecular modeling and molecular dynamics simulations have contributed to the understanding of the structure of the diastereomeric complexes, complexation thermodanymics and the visualization of their structures. As part 1, the present review highlights contributions to the understanding of the enantiorecognition mechanisms of polysaccharide as well as cyclodextrin chiral selectors published between 2016 and mid 2019.