Linkage positions in oligosaccharides may be obtained by FAB CAD MS/MS (Fast Atom Bombardment Collision Activated Dissociation Mass Spectrometry/Mass Spectrometry). Acetylated derivatives of the linkage-isomeric trisaccharides exhibited more useful product ion patterns than the free trisaccharides and provided specific fragmentation patterns according to linkage positions. The reason for the useful linkage dependent spectra patterns of acetylated forms is related to the ability of each linkage in the oligosaccharides to absorb different levels of collision energy and rotational freedom of the individual glycosidic linkage.