Xanthones are well known for their interesting phytochemical properties, which make them attractive to the pharmaceutical and medicinal industry. We have therefore developed a method to analyse the major xanthones in Garcina mangostana. The xanthones were extracted by pressurized liquid extraction with ethanol and separated at the semi-preparative scale by centrifugal partition chromatography (CPC) with a biphasic solvent system consisting of heptane/ethyl acetate/methanol/water (2:1:2:1, v/v/v/v). A CPC-electrospray ionisation MS coupling was performed and used to simultaneously separate and identify the compounds. Thanks to a variable flow splitter and an additional stream of ethanol/1 mol L(-1) ammonium acetate (95:5, v/v), all the compounds were ionised, detected and monitored whatever the solvents used in mobile phase for the CPC separation. The dual mode or elution-extrusion which are less solvent-consuming and faster than the elution mode were used without loss of ionisation and detection.