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Summary: New “saccharide polymers” were synthesized via free radical polymerization. The saccharide compounds in copolymerisation reactions were 2,4,6‐tri‐O‐acetyl‐3‐deoxy‐D‐erythro‐hex‐2‐enono‐1,5‐lactone (1), (Ac‐GEL 1) and 2,4,6‐tri‐O‐benzoyl‐3‐deoxy‐D‐erythro‐hex‐2‐enono‐1,5‐lactone (2), (Bz‐GEL 2). These sugar monomers are easily obtained with high yield in a one step reaction from glucono‐δ‐lactone. They have a pyranoid structure containing an endocyclic double bond and they are electron acceptor compounds. Copolymerization reactions were carried out in solution and in substance. Copolymers with different sugar contents and low as well as high molecular weights were obtained. The structures and the compositions of the soluble saccharide polymers were established by elemental analysis, polarimetry, FTIR spectroscopy, 1H and 13C NMR spectroscopy. Some characteristic properties, e.g., molecular weight, optical rotation and copolymerization parameters are reported.