A series of novel polyesters containing dioxane moieties in their main chains were synthesized by the bulk polycondensation of trans-2,5-bis-(hydroxymethyl)-1,4-dioxane with various aliphatic dicarboxylic acid chlorides. The obtained polyesters, analyzed by differential thermal analysis, possessed crystallinity, the melting point of which exhibited a weak odd-even effect on the methylene unit number and a small decreasing trend with an increase in the methylene unit number. These properties were compared with those of similar polyesters bearing cyclohexane moieties, and it was found that the rigidity of the dioxane moiety plays an important role in enhancing the effective packing of the corresponding polymers.