Capillary electrophoresis (CE) is a powerful tool for the analysis of chiral compounds of pharmaceutical interest. The separation of enantiomers can be achieved using a chiral environment responsible for the diastereoisomers formation (stable or labile in the indirect or direct separation method, respectively). A wide number of chiral selectors have been employed in CE and among them cyclodextrins or their derivatives and antibiotics are the most used stereoselective agents. The review surveys the chiral separation of drugs using the above mentioned chiral selectors by CE. The main parameters influencing the enantioresolution, e.g., chiral selector type and concentration, buffer type, concentration, pH, organic modifier as well as the capillary temperature are discussed. Finally some selected applications to real samples such as pharmaceutical formulations, serum, urine are also discussed.