Abstract: pH-zone-refining counter-current chromatography(pH-zone-refining CCC), based on the development of high speed counter-current chromatography(HSCCC), has been widely used for purification of alkaloids. Due to high sample quantity, perfect separation efficiency, easy collection of impurities, on-line pH monitoring, and highly-concentrated fractions, pH-zone- refining CCC has been widely applied in many researches and practice. As important natural products, alkaloids have strong biological activities and exert good treatment effect to many diseases. This paper introduces the pH-zone-refining CCC and its successful application in separation of alkaloids instances.