The structural elucidation of oligosaccharides remains a major challenge. Mass spectrometry provides a rapid and convenient method for structural elucidation on the basis of tandem mass spectrometry. Ions are commonly selected and subjected to collision-induced dissociation (CID) to obtain structural information. However, a disadvantage of CID is the decrease in both the degree and efficiency of dissociation with increasing mass. In this chapter, we illustrate the use of infrared multiphoton dissociation (IRMPD) to obtain structural information for O-and N-linked oligosaccharides. The IRMPD and CID behaviors of oligosaccharides are compared.