Capillary electrophoresis (CE) represents one of the major techniques not only for analytical scale enantioseparations but is also a powerful tool for a better understanding of the fine mechanisms of enantioselective intermolecular recognition.The major advantages of CE from the viewpoint of enantioselective molecular recognition studies are the following: 1.CE allows very fast screening of selector-selectand pairs.2.The high peak efficiency in CE permits to observe enantioselective features in selector-selectand interactions which are invisible by other techniques.3.A small thermodynamic selectivity of recognition can be transformed into a high separation factor in CE.4.CE is very flexible technique for adjustment of enantioseparation.