Various modes of capillary electrochromatography (CEC) for the separation of enantiomers on immobilized cyclodextrin derivatives are described. The following techniques have been used: (i) open-tubular electrochromatography (o-CEC), (ii) packed electrochromatography (p-CEC) and (iii) monolithic electrochromatography (rod-CEC). Three different strategies to prepare enantioselective cyclodextrin-coated chiral monoliths are described. The advantages and disadvantages of the various methods are outlined.