Resolution of racemic compounds is one of the potential ways of obtaining both enantiomers. Among several resolution techniques in the past few decades, direct enantioseparation by high-performance liquid chromatography (HPLC) has significantly advanced, and a large number of chiral stationary phases (CSPs) for HPLC have been developed using both chiral small molecules and polymers with chiral recognition abilities. In this tutorial review, after describing the brief history and general view of CSPs, special emphasis will be placed on the studies involving the development and application of polysaccharide-based CSPs in our group.