The development of polymers based on monomers from renewable feedstock, and more specifically from carbohydrates, is a steadily growing field of interest because of the properties that can generate these unique structures. They are promising materials with novel technical possibilities and improved properties, such as biocompatibility and biodegradability1,2 2,4:3,5-Di-O-methylidene-D-glucitol is a carbohydrate-based diol suitable for the preparation of linear polycondensates. This compound is readily prepared from Dgluconolactone by acetalization and subsequent reduction.4The fused bicyclic dioxolane rings provide rigidity to the molecule making it an interesting candidate for replacing aromatic rings in conventional aromatic polyesters. A series of copolyesters made of dimethylterephthalate, 1,6-hexanediol and 2,4:3,5-di-O-methylidene-D-glucitol (PHxGlxyT) with gludioxol contents ranging between 5 and 32 mol % were synthesized by melt polycondensation and characterized by NMR and FTIR spectroscopy, GPC and viscosimetry. The copolyesters had a random microstructure and number-average molecular weights ranging from 5,000 to 15,000. The influence of the content in gludioxol on the synthesis results, structure and thermal properties of the novel copolyesters was comparatively evaluated and discussed.