Human milk oligosaccharides (HMOs) are important biomacromolecules in human body, which involve prebiotic activity, antiadhesive and antimicrobial effects, mediating intestinal epithelial cell responses, modulating of immune responses, and provide essential nutrients for brain development. HMOs are therefore expected to be very useful for the development of drugs, which are effective for protection of infants from harmful infections. To gain more insight into mechanism in human bodies, the development of an effective method to synthesize a series of minor but useful fucosylated oligosaccharides for further biological studies is in urgent need. In this special report, the function and applications of human milk oligosaccharides were discussed as well as the synthetic methods of these valuable biomolecules.