Based on the research work from Prof. Okamoto’s group, polysaccharide-derived and silica-supported chiral stationary phases were introduced in the 1980s. They are considered as the first choice of chiral stationary phases (CSPs) for enantiomer separations by liquid chromatography and supercritical fluid chromatography. A considerable number of publications have reported and reviewed the applications of these CSPs by scientists working in the field of enantioseparations. Although most separations can be achieved with a reduced number of columns and mobile phases, there remains a need for unique selectivities that allow the resolution of certain challenging isomers or their impurities. This is where the “secondary” column set can step in. Chlorinated solvents are usually submitted to a more rigorous control due to environmental restrictions. Nevertheless, their use at analytical level may be allowed in most laboratories, provided that their waste residues are treated appropriately.