Abstract: A new micellar capillary electrophoresis method was developed for simultaneous separation and determination of psoralin, coryfolin, corylifolinin, psoralidin and corylin in Psoraleae Fructus within 23 minutes by using a Na₂B₄O₇ (20 mmol/L) buffer (adjust pH to 9.31 with NaOH) consisting of 25% (v/v) acetonitrile, 25 mmol/L SDS in the instrumental conditions of the separation voltage of 20 kV, detector wavelength of 300 nm, and injection of 5 s at 3.448 kPa. The developed method was applied to the determination of five compounds in Psoraleae Fructus and its preparations with the recovery in the ranged between 95.4%−104.7% and the relative standard deviation of less than 5.0%. So this new method is accurate and reliable, and can be used for the quality control of Psoraleae Fructus and its preparations.