A micellar electrokinetic capillary chromatography (MECC) method for the separation and determination of five components, glycyrrhizic acid (GA), glycyrrhetinic acid (GTA) and 3,4'-dimethoxy-5-hydroxychalone, fermononetin and isoliquiritigenin, in extracts of Glycyrrhiza uralensis Fisch root was developed. Migration behavior of these analytes was studied by the systematic examination of the berate and sodium dodecyl sulfate (SDS) concentrations in the run buffer. The optimum separation for these analytes was achieved using 10 mmol l(-1) of tetraborate and 25 mmol l(-1) of SDS as the running buffer, with 17 kV of applied voltage. All experiments were performed using a 50.0 cm (42.4 cm effective length)X75 mu m I.D. of fused-silica capillary. The apparent pK(a) values of GA and GTA and the binding constants for the association between the above five analytes and SDS were calculated in this study. A comparison of the extraction efficiency for GA and GTA from Glycyrrhiza uralensis Fisch root was made using ethanol, distilled water and chloroform as extraction reagents, respectively. These results provided very useful information to select the proper solvent to extract the desired components in Glycyrrhiza uralensis Fisch. The MECC method established in this paper was employed to analysis the above five active components. (C) 1999 Elsevier Science B.V. All rights reserved.