Abstract: Micellar chromatography was chosen for the separation of coptisine, jatrorrhizine, palmatine and berberine. Several factors affecting the separation selectivity of solutes——stationary phase, concentration of micelle, ratio of organic modifier and pH——were investigated. Experimental evidences indicate: the main effective factors are the polarity of stationary phase and the concentration of micelle. At room temperature, the efficiency of micellar chromatography can be improved only by adding methanol into the mobile phase. A reversed-phase system of μ-Bondapakphenyl column with a micellar solution of 3.5% sodium dodecyl sulfate/0.1 N tartaric acid-methanol (30:70) as mobile phase was used to determine coptisine, jatrorrhizine, palmatine and berberine in 8 rhizoma Coptidis and cortex Phellodendri and in 8 Chinese patent medicines.