A practical solution of qualitatively analyzing quaternary alkaloids in coptis-scute herb couple by electrospray ionization mass spectrometry(ESI-MS)Was developed.Without the complicated pretreatment of sample,the active ingredients including berberine, palmatine, coptisine, jatrorrhizine, epiberberine, and columbamine were identified and some relative content changing rules of alkaloids in coptis-scute couple were summarized in this article. The overall profiles of the complex extracts were obtained.After adding an internal standard(rutaecarpine), semi-quantitative analysis was performed and the result indicates that the actual content of alkaloids was decreased by increasing the amount of scute.Based on the data obtained by high-performance capillary electrophoresis(HPCE),the feasibility of semi-quantitative analysis by ESI-MS WaS further proved.