Per-O-acetylated methyl glycosides of D-xylan-type di- and trisaccharides were studied by mass-analysed ion kinetic energy (MIKE) and collisionally induced dissociation (CID) mass Spectrometry using protonated ammonia and methylamine, respectively, as reaction gases in chemical ionization (CI). The oligosaccharides form abundant cluster ions, [M + NH 4] + or [M + CH 3NH 3] +, and the main fragmentation of these ions in the MIKE and CID spectra is the cleavage of interglycosidic linkages. Thus, CI (NH 3) or CI (CH 3NH 2) spectra in combination with the MIKE or CID spectra allow the molecular masses, the masses of monosaccharide units and the branching point in oligosaccharides to be established. In the case of disaccharides, it is possible to distinguish the (1 2) linkage from the other types of linkages.