The separation of the enantiomers of amphetamine, methamphetamine, ephedrine, pseudoephedrine, norephedrine and norpseudoephedrine in a single run via micellar electrokinetic capillary chromatography (MECC) is described. The procedure, which involves preliminary derivatization with 2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl isothiocyanate (GITC) followed by MECC analysis, is far superior with respect to both resolution and speed of analysis versus similar efforts utilizing high-performance liquid chromatography. The MECC separation was obtained at 20 kV on a 48 cm x 50-mu-m I.D. (26 cm length to detector) capillary at 30-degrees-C using a run buffer consisting of 20% methanol and 80% sodium dodecyl sulfate (SDS) solution [100 mM SDS, 10 mM phosphate, 10 mM borate (pH 9.0)]. The effects of organic modifier type, organic modifier concentration, voltage, temperature and SDS concentration on the resolution of the GITC derivatives are described. The application of the above methodology to forensic samples is presented.