X-ray diffraction analysis revealed that the furan-based copolyesters are semicrystalline materials and they crystallize into β-form crystals. The study found that the diol chain length within the hard segments had an effect on the crystalline structure of the copolyesters. As the chain length increased, the spacing between the planes in the atomic lattice (d) also increased. Additionally, the degree of crystallinity (Xc') decreased as the number of carbon atoms within α,ω-ALD increased. This is likely due to the decrease in chain regularity and greater capacity of rotational motions of polymer chains which may hinder the ability to form crystal structures.