The transesterification of divinylsebacate with glucose in pyridine was catalyzed by Alcaligenes sp. lipase at more than 99% of conversion rate. The sugar ester could be polymerized in dimethylformamide with 2,2＇-azobis(isobutyronitrile) to give the new branched polymer, poly (6-O-vinylsebacyl-D-glucose), having molecular weight (Mn) of 11,000.