The polyol ester derived from palm oil polymers is a promising material for utilizing it as a polymeric drug carrier due to its natural and biocompatible properties. In this study, the palm oil‐based diol is used as a precursor for developing the polyol ester via the transesterification‐alcoholysis reaction of the diol with triethanolamine and lithium hydroxide. Preliminary results showed that the polyol ester displayed high hydroxyl value at 182.51 mg KOH/g with the yield reached more than 90%. Meanwhile, its molecular weight was around 5,000 Dalton. The appearances of ester (C–O) between 1,300 and 1,000 cm−1 in the Fourier transform infrared (FTIR) spectra have confirmed the hydrolyzable ester structure of the polyol ester. Consequently, the δH‐ and δC‐NMR spectra also confirmed the presences of the ester proton (i.e., ‐COO–CH2‐) and the ester carbons (i.e., ‐CH2CH2CO(O)C‐, ‐CH2COO‐, ‐CH2C(O)OC‐). Thermogravimetric analysis of the polyol ester displayed three stages of maximum decomposition temperature (Tmax): 203.56°C, 362.79°C, and 481.91°C. Differential scanning chromatography (DSC) analysis indicated that the glass transition temperature (Tg) of the polyol ester was found between −3.27 and 7.5°C. As a result, the analyses affirmed that this polyol ester is a hydrolytically degradable polymer due to the presence of its hydrolyzable ester bonds. Its low molecular weight and low‐melting biodegradable properties could show a faster degradation compared to the higher molecular weight synthetic polymers. Thus, the characteristic of the developed polyol ester demonstrates promising physicochemical and good thermal properties, which makes it a potential candidate for a polymeric drug delivery system.