Abstract Some important precursors (1,6‐anhydrous‐2‐deoxy‐2‐azido‐β‐D‐glucopyranose (3), 1,6‐anhydrous‐2‐deoxy‐2‐ azido‐3,4‐di‐O‐benzyl‐β‐D‐mannopyranose (5), 1,6:2,3‐dianhydrous‐β‐D‐glucopyranose (6), 1,6‐anhydrous‐3‐deoxy‐3‐azido‐β‐D‐glucopyranose (10) and 1,6‐anhydrous‐2,4‐di‐O‐benzoyl‐β‐D‐glucopyranose (11)) for complex oligosaccharide synthesis were readily prepared from a green starting material 1,6‐anhydrous‐β‐D‐glucopyranose in one or two steps with moderate to high yields. These improved methods established herein will greatly facilitate the assembly of some complex oligosaccharides for the biological study.