A series of 2-C-branched glycosyl triazoles including triazole-tethered oligosaccharides and glycopeptides were synthesized in one pot from 1,2-cyclopropanated sugars or 2'-acetonyl-2-O-Ts-C-furanosides, NaN3, and alkynes using PEG-400 as a single solvent. Nucleophilic ring-opening azidation of 1,2-cyclopropanated sugars (or 2'-acetonyl group 1,2-migration-azidation of C-furanosides) obtained glycosyl azides, which upon reaction with alkynes under CuAAC conditions achieved glycosyl triazoles in good yields and high stereoselectivity without the need to change the solvent and isolate any intermediates.