Being the first member in the family of nanocarbon superstructures, fullerene C₆₀ (refers to C₆₀ hereafter) continues to be a research focus in physics, chemistry, materials science, biology and life science. The readily available functionalization methods that can be realized on C₆₀ further expand the potential applications of C₆₀ in various fields. Carbohydrates distribute widely in a variety of forms in mammalian animals and the glycan-protein interactions play important roles in many biological processes. Covalently attaching sugar units to C₆₀ yields glycofullerenes, which exhibit interesting physicochemical properties and biological activities. Here, we give a comprehensive review on the syntheses, properties and applications of this novel class of C₆₀ derivatives. Directions in which efforts should be devoted to in near future have also been discussed.