Abstract: A micellar electrokinetic capillary chromatography method was developed for the determination of anthraquinones in rhubarb and its preparation. The effects of pH value of buffer system, the concentration of sodium dodecyl sulfate (SDS), the organic modifier and its concentration on the separation selectivity were discussed. The results indicated that the anthraquinones were baseline separation under the 10 mmol/L borate buffer at pH 9.5 with 25 mmol/L SDS and 20%(V/V) acetonitrile. The calibration curves exhibited good linearity between the concentrations and the peak area of the three components. The relative standard deviations (RSD) of migration time and peak areas were 3.45% and 4.86%, respectively.