This study reports on the development and preliminary validation of a capillary electrochromatographic (CEC) method for the enantioselective impurity profiling Of D-ephedrine. As chiral selector a novel low-molecular-weight strong chiral cation exchanger, based on penicillamine sulfonic acid, immobilized on thiol-modified silica particles (3.5 mum) was employed. Under optimized conditions, the ephedrine enantiomers were separated on this chiral stationary phase (CSP) with an enantioselectivity of 1.11, an average efficiency of 321 550 plates per meter, and a resolution value of 4.77. A preliminary method validation was carried out to demonstrate the applicability of CEC for enantiomeric excess (ee) determination. Run-to-run repeatabilities (n = 5) reached relative standard deviation values (RSD) of 0.18 and 0.19% for the migration times of L- and D-enantiomer, respectively, 0.3% for the resolution, and about 0.9% for the peak efficiencies. An approach called self-internal standard method was utilized to measure a standard calibration curve. Excellent linearity with a correlation coefficient of R-2 = 0.9998 was found for samples with concentrations in the range between 0.03 and 5 mg(.)mL(-1) D-ephedrine spiked with L-ephedrine at a constant concentration of 0.2 mg(.)mL(-1). The high loadability of the investigated CSP and good peak sensitivity allowed us to determine less than 0.1 % enantiomeric impurity with good accuracy. The limit of detection (LOD) for the L-enantiomer in a 3 mg(.)mL(-1) D-ephedrine solution was found to be 0.035% (S/N = 3) and the limit of quantitation (LOQ) 0.058% (S/N = 5). For L-ephedrine samples the strong cation-exchange (SCX)-type CSP with opposite configuration was utilized so that the enantiomeric impurity eluted before the main component peak yielding similar results in terms of separation and validation. Based on these results, the presented nonaqueous CEC methods are assessed as principally suitable for ee determination of ephedrine in terms of repeatability and method sensitivity.