Capillary electrophoresis (CE) is a versatile and flexible technique for analytical enantioseparations. This is due to the large variety of chiral selectors as well as the different operation modes including electrokinetic chromatography, micellar electrokinetic chromatography, and microemulsion electrokinetic chromatography. The chiral selector, which is added to the background electrolyte, represents a pseudostationary phase with its own electrophoretic mobility allowing a variety of different separation protocols. The present chapter briefly addresses the basic fundamentals of CE enantioseparations as well as the most frequently applied chiral selectors and separation modes. The practical example illustrates the separation of the enantiomers of a positively charged analyte using native and charged cyclodextrin derivatives as chiral selectors.