This paper reports a new capillary zone electrophoresis method for the simultaneous chiral determination of the enantiomers of N,N-dimethylamphetamine (DMA), methamphetamine (MA), ephedrine (E), pseudoephedrine (PE) and methylephedrine (Me-E). In this study, a number of electophoretic parameters were examined and optimized including the choice of chiral selectors, the use of short-chain tetraalkylammonium cations, the effect of chiral selector concentration, buffer concentration, applied voltage and capillary temperature. Heptakis(2,6-di-O-methyl)-beta-cyclodextrin (DM-beta-CD) and tetrabutylammonium (TBA) being the best chiral selector and buffer cation, respectively, the optimized electrophoretic conditions were found to be: 20 mM DM-beta-CD, 50 mM TBAPO(4) at pH 2.5, applied voltage at 30 kV and temperature at 25 degrees C. Under the optimized conditions, all analytes were well separated with resolution factors between 3.3 and 24.0 achieved. Using phentermine as an internal standard, the intra-day (n=8) precisions for the relative migration times and peak areas of all analytes were below 1.09%, while the inter-day precisions (n=12, 6 days) for the relative migration times and peak areas of all analytes were under 3.77%. This method has been applied to the measurement of the enantiomeric purities of the seized DMA samples. The result of the measurement could provide important clues about the possible synthetic pathways of these samples.