A maltotriose glycosyl azide bearing a β-anomeric azide on the reducing-end glucose of the α1-4-linked trisaccharide. The anomeric azide can be coupled to alkynes via CuAAC or to DBCO and related strained alkynes via copper-free click chemistry, forming stable 1,2,3-triazole linkages. Used as a click-chemistry building block for the synthesis of maltooligosaccharide-presenting glycoconjugates and as a probe for α-glucan-recognizing proteins.