The article gives an overview of the state of the art of capillary electrophoresis in the field of chiral separations. The review covers basic principles of separation of enantiomers by electromigration methods. Various separation modes, various chiral selectors, and separation mechanisms responsible for chiral recognition are shown. Factors affecting the resolution, such as concentration of chiral selector(s), electrolyte composition, its concentration, pH, ionic strength, and addition of organic modifiers, are discussed. Possibilities to use mathematical or semiempirical approaches for optimization of the separation system are demonstrated on examples of the most frequently used chiral selectors - cyclodextrins.