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Human milk oligosaccharides (HMOs), which are renowned for their biological activity in the gastrointestinal tract, are of special interest for infant nutrition. So far, little is known on the gastrointestinal fate of these oligosaccharide structures. Our recent studies therefore aimed at an advanced understanding of the gastrointestinal metabolization of HMOs. Capillary electrophoresis with laser-induced fluorescence detection coupled to a mass spectrometer was used for the analysis and identification of HMOs in breast milk and oligosaccharides in the feces of breast-fed babies. For breast-fed babies a gradual change in fecal oligosaccharide profile was found during the first six months postpartum. Three continuous stages of fecal oligosaccharide profiles were defined, comprising either the presence of the genetically determined HMO-profile of the breast milk consumed or a set of remaining acidic HMOs (stage 1), the presence of oligosaccharides carrying blood group determinant groups (stage 2) and oligosaccharides characteristic for follow-up feeding when solid food is introduced (stage 3). Monitoring the gastrointestinal fate of HMOs pointed to an individual-dependent gastrointestinal adaptation to enteral food during the postnatal period, mainly depending on the HMO-composition in breast milk and gestational age. Moreover, the postnatal development of fecal oligosaccharide profiles can be related to the development of the gastrointestinal microbiota reported elsewhere.