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In this work, eight compounds from Phellodendron chinense were separated and purified by pH‐zone refining counter‐current chromatography and traditional counter‐current chromatography coupled with online‐storage inner‐recycling counter‐current chromatography (IRCCC). The pH‐zone‐refining mode was adopted for separating 2.0 g of crude extract with the solvent system of chloroform–methanol–water (4:3:3, v/v), in which 10 mM hydrochloric acid and 10 mM triethylamine were added in the stationary and mobile phases, respectively. Meanwhile, traditional counter‐current chromatography coupled with online‐storage IRCCC separation was performed by the solvent system of n‐hexane‐ethyl acetate‐methanol‐water (5:5:2:8, v/v). Finally, eight compounds, including six alkaloids as 6‐methylpiperidin‐2‐one(1), isoplatydesmine(4), berlambine(5), epiberberine(6), palmatine(7), berberine(8) and two phenolic acids as ferulic acid(2), isoferulic acid(3), were successfully obtained using these three different CCC modes with the purities over 95.0%. [ABSTRACT FROM AUTHOR]