Novel ABA and star amphilphilic block copolymers of poly(vinyl sugars) with biodegradable hydrophobic poly(epsilon-caprolactone) segments are presented. They were prepared by a combination of ring-opening polymerization of epsilon-caprolactone and atom-transfer radical polymerization of methacrylate-bearing isopropylidene-protected galactose. Subsequently, the protecting groups of the sugar fragments were removed by treatment with 80% formic acid.