ABSTRACT:A new 1,6-anhydro-sugar monomer carrying 2,3-di-O-alkyl chains, l,6-anhydro-4-O-benzyl-2,3-di-O-dodecyl-P-o-mannopyranose (ABDDM) was synthesized by regioselective protection, and polymerized in cationic conditions, giving stereoregular (1--->6)-a-o-mannopyranan derivative. Copolymerization of ABDDM with I ,6-anhydro-2,3,4-tri-O-benzyl-P-o-glucopyranose (ATBG) was carried out, and monomer reactivity ratios were calculated by the Kelen-Tiidos method, showing rAaooM=0.51 and rArnG=0.54.