Abstract: Enantiomers of bioactive molecules often differ in potency, toxicity, metabolism, and pharmacological actions. Capillary electrochromatography (CEC) is an emerging separation technique being investigated for use in chiral separations. CEC is a hybrid of HPLC and CE. CEC combines the electrophoretic mobility of CE with the partitioning mechanisms of HPLC. In this overview, several resolution mechanisms commonly used in CEC and the main parameters influencing the selectivity of the chiral separation will be discussed. Current applications of CEC in chiral separations of pharmaceuticals will be provided for each type of resolution mechanism. Finally, the advantages and limitations of CEC will be described, followed by the future outlook for CEC