A series of biobased “short-long” chain aliphatic polyesters having high molecular weight were successfully synthesized using dimethyl sebacate and diols with different carbon chain lengths via a two-step melt-polycondensation method by using titanium butoxide as a catalyst. The diols chain length and its odd-even effect on the structure–property relationship, crystallinity, and thermomechanical properties of the polyesters were systemically investigated. The synthesized polyesters displayed weight-average molecular weight between 23,600 to 72,900 g/mol and a maximum intrinsic viscosity of 0.933 dL/g. With increasing the diol chain length, the molecular weight of the polyesters increased linearly, except for poly(butylene sebacate) (PBS). Altogether, the “odd-even” effect of the diol chain on the crystalline (T_c)/melting temperature (T_m), and melting/ crystallization enthalpies of the polyester's were observed. Poly(pentylene sebacate) (PPeS) has the highest weight-average molecular weight of 72,900 Da, T_m of ∼55.4°C, degradation temperature (T_d,max) of about 404°C, and highest storage modulus (E′ at 25°C) of 661 MPa compared to other short-chain polyesters. PBS and PPeS showed the appearance of sharp intensity peaks from XRD diffraction patterns, indicating higher crystallinity in the material, in accordance with crystallization enthalpies (ΔH_c) values from the differential scanning calorimetry (DSC) thermograms. These fabricated biobased polymers with 100% bio-content, low melting temperature range, rapid crystallization, and high thermal stability suggest good processability and can offer an alternative option to nonrenewable thermoplastic polyesters for potential applications.