Capillary electrochromatography is a miniaturized technique offering some advantages over conventional ones in separation science. It combines the best features of capillary zone electrophoresis (high efficiency of separation) and liquid chromatography (high selectivity). Because of the low flow rates, minute volumes of mobile phases can be applied, and therefore, it can be considered a green analytical technique. Capillary electrochromatography has been successfully used to separate many classes of compounds, including peptides, proteins, drugs, antibiotics, pollutants, enantiomers, etc. In this overview chapter, the main features of this technique are summarized. Its potential for the separation of enantiomers of chiral compounds and the main chiral stationary phases employed are presented. Finally, some selected applications in this field, reported in the literature in the period 2020–2024, are presented.