Human milk oligosaccharides (HMOs) are the third most abundant solid component after lactose and lipids of breast milk. All mammal milk contains soluble oligosaccharides, including neutral milk oligosaccharides (NMOs) without sialic acid (Sia) moieties and acidic oligosaccharides or sialylated milk oligosaccharides (SMOs) with Sia residues at the end of sugar chains. The structural, biological diversity, and concentration of milk oligosaccharides in mammalian milk are significantly different among species. HMOs have multiple health benefits for newborns, including development of immune system, modification of the intestinal microbiota, anti-adhesive effect against pathogens, and brain development. Most infant formulas lack oligosaccharides which resemble HMOs. Formula-fed infants perform poorly across physical and psychological wellbeing measures and suffer health disadvantages compared to breast-fed infants due to the differences in the nutritional composition of breast milk and infant formula. Of these milk oligosaccharides, SMOs are coming to the forefront of research due to the beneficial nature of Sia. This review aims to critically discuss the current state of knowledge of the biology and role of SMOs in human milk, infant formula milks, and milk from several other species on gut and brain health of human and animal offspring.