Infrared multiphoton dissociation (IRMPD) of alkali metal-coordinated oligosaccharides was obtained in a Fourier transform mass spectrometer. Fragmentation of the oligosaccharides was observed for Li+- and Na+-coordinated species. For larger alkali metal ions (K+, Rb+, and Cs+), the major products were the alkali metal ions. IRMPD experiments were performed on milk oligosaccharides, and the dissociation thresholds were determined. The threshold values were found to differ for the isomers. It is suggested that the threshold may be useful for differentiating isomeric compounds. Additionally, oligosaccharide alditols from biological samples were analyzed. Comparison of the collision-induced dissociation (CID) and IRMPD spectra of oligosaccharide alditols revealed that IRMPD could be used as a complementary method to obtain structural information.