The synthesis of HO-protected poly(glycolic acid-co-gluconic acid) and poly(L-lactic acid-co-glycolic acid-co-gluconic acid) by copolymerisation of L-lactide and 3-(1,2-3,4-tetraoxobutyl-diisopropylidene)-1.4-dioxane-2,5-dione (DIPAGYL) is reported. The resulting polymers were characterized by size exclusion chromatography, FT Infrared, nuclear magnetic resonance. differential scanning calorimetry and X-ray diffractometry. The composition of reaction media and the reactivity ratios of the two cyclic monomers were determined at low conversion and indicated random distributions of lactyl and gluconoglycolyl constitutive units. X-ray diffraction data showed semi-crystalline morphology, as observed for poly (lactide) stereocopolymers containing more than 90% of L-enantiomer. Deprotection of the isopropylidene-protected side chain OH was possible under acidic conditions and yielded copolymers with various degrees of hydroxylation. Deprotection of the 5-6 OH groups was fast and complete whereas that of 3-4 ones was partial and occurred at the expenses of partial degradation of the aliphatic polyester chains. T-g increased with the number of hydroxyl functions, a feature attributed to the formation of hydrogen bonds. Comparison is made with features reported previously for analogs derived from DL-lactide. (c) 2006 Elsevier Ltd. All rights reserved.