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In present work,we report a facile access to prepare stereopolyester with tunable geometric structure through the organocatalytic copolymerization of cyclohexene oxide (CHO) with norbornene anhydride (NA) stereoisomers.(see Scheme 1) The focuses have been devoted to determine the influence of NA configuration on the copolymerization under various conditions,in particular on the stereochemistry of resulting polyester as well as their properties.Moreover,to evaluate versatility of resulting polyester,a free radical-mediated thiol-ene reaction was employed to testify the capacity.