Different approaches to the enantiomeric separation of sixteen derivatized di-and tripeptides, having one or two chiral centers, by means of capillary electrophoresis have been examined. The approaches were: direct separation using cyclodextrin (CD), vancomycin or teicoplanin and indirect separation. The highest plate numbers, 10(6) plates/m, were obtained with CD and the indirect method. The maximum resolution was 3 with CD and 11 when using the indirect method. The antibiotics gave somewhat lower plate numbers, 0.5.10(6) plates/m, but the resolution was high, up to 38. All examined peptides, except Leu-Ala, Leu-Leu and Arg-Gly, were fully resolved with the antibiotics as chiral selectors. The three remaining peptides were fully resolved when using the indirect method. (C) 1997 Elsevier Science B.V.