This study involves the quantitative analysis of high free fatty acid crude palm oil, the separation of palmitic acid and synthesis of palm palmitic acid-based bioplastic. Synthesis of dimethyl 2-tetradecylmalonate (DMTDM) using methyl palmitate (MP) with sodium hydride (NaH) in the presence of reactive solvent of dimethyl carbonate (DMC) was carried out. The reaction conditions comprise at a mole ratio of MP: DMC: NaH: dimethylformamide (DMF) (0.1:2:0.25:1) at 60 °C for 14 h with 88.3 ± 1.4% yield. FTIR spectra of DMTDM showed the ester carbonyl group at 1740 cm-1. The polymerization of DMTDM with 1,6-hexandiol or 1,12-dodecandiol was carried out using titanium (IV) isopropoxide Ti(OiPr)4 as the catalyst and reaction time of 24 h. The results showed that the poly(dodecyl 2-tetradecylmalonte) (PDTDM) exhibited good thermal properties compared to poly(hexyl 2-tetradecylmalonte) (PHTDM). The increase of the chain length of diol in PDTDM improved the thermal properties of polyester with glass transition, Tg of 13 ºC and melting point of 51 ºC with a molecular weight of 12508 Da and polydispersity index (PDI) of 1.4. In general, the synthetic polyesters can be used as internalplasticizer in bio-based industry.