The chemical structure of the copolymers was evaluated using 1 H and C NMR spectroscopy, which confirmed that the copolyesters had the expected chemical structure. Additionally, the segmental composition of the copolyesters was calculated and found to be similar to theoretical values, indicating good control over the synthesis process. The content of hard segments in the copolyesters was also observed to increase with an increasing number of carbon atoms in the α,ω-ALD. This is likely due to the removal of diols with lower boiling points from the reaction mixture under the applied vacuum and high temperatures. Furthermore, the number averaged molecular weight of the copolyesters calculated from 1 H NMR increased with an increasing number of carbon atoms in the α,ω-ALD.