An overview is given of the development of the variety of chiral stationary phase materials that are available today for the direct separation of enantiomers by different chromatographic methods. Applications of these range from trace analytical determinations of enantiomeric composition in biological materials to large scale preparative isolation of enantiopure compounds of industrial importance. These chromatographic techniques are also of interest for studies of mechanism and dynamics, like enantiomerization processes due to chiral inversion taking place in thermally labile chiral molecular structures.