A CZE method using a complex of 2.5 mM Cu(II)-L-lysine (molar ratio is 1:2) as additive in a run buffer solution composed of Tris-H(3)PO(4) (pH 4.5) was developed for the simultaneous determination of ephedrine and pseudoephedrine within 4 min. The effects of pH, composition, and concentration of run buffer as well as the composition and concentration of the Cu(II)-L-lysine complex on the separation were investigated. The linear ranges for the determination of ephedrine and pseudoephedrine were 15.0-225.0 and 20.0-250.0 mg/L with LODs both of 5.0 mg/L. Satisfactory result for the determination of ephedrine and pseudoephedrine in Ephedrae Herba from different producing area was obtained by the proposed method. Ephedrine and pseudoephedrine were separated effectively with each other and with the other compounds in the sample. The RSD for the determination of the two constituents in the samples varied from 1.82 to 2.76%, and the recovery ranged between 95.0 and 104.0%.