Glycoconjugate polymers with poly(vinyl alcohol) (PVA) backbone were synthesized via a chemoenzymatic method. The sugar alcohols of maltose and lactose were submitted to transesterification in the presence of lipases. The esterification was achieved with high selectivity and yield, and the resulting maltitol and lactitol 6-vinyl sebacates were polymerized by a conventional radical initiator with hydrogen peroxide and ascorbic acid. The glycoconjugate polymers carrying alpha-glucose and beta-galactose as recognition signals showed the biological activity such as lectin recognition abilities and hepatocyte adhension. The biodegradability of these polymers was modest but higher than PVA.