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The silver ionic complexes of xanthone glycosides were studied by ESI-MS/MS in the positive ion mode. The fragmentation pathways of silver ionic complexes under collisioninduced dissociation (CID) were investigated and the differences in MS/MS spectra of different silver ionic complexes of xanthones were correlated to the characterization of saccharide and the coordination pattern of silver ion with xanthones, including the glycosilation position and linkage type of disaccharide (1-2 and 1-6 linkages).