An improved method for the synthesis of per-O-acetylated C-1-hydroxyglycopyranose was developed by hydrolysis of per-O-acetylated glycopyranosyl α-chlorides derived from sugars with C-2 axial acetates for example l-rhamnose and d-mannose. 2,3,4-Tri-O-acetyl-α-l-rhamnopyranose crystallized in tetragonal space group I4, a rare phenomenon in carbohydrate literature. The three dimensional packing of the molecule with the help of regular hydrogen bond and C-H···O interactions resulted in the formation of porous framework showing channels with pore size 7 Å. © 2013 Elsevier Ltd. All rights reserved.