Enantiomeric separation is an important subject in analytical chemistry and many other areas, including pharmaceutics, medicinal sciences, etc. A new separation mode which combines the advantages of capillary electrophoresis and liquid chromatography is called capillary electrochromatography (CEC). CEC increases both of the efficiency of separation and the selectivity of enantiomeric separation. Most of the chiral stationary phases for CEC are inherented from chromatography. In this review report, the operations and advantages of capillary electrochromatography are described briefly, then the developments and applications of chiral stationary phases are discussed.