Research and development of palm-based polyols have been intensively carried out to improve their features and characteristics appropriate for their required applications. The physicochemical properties of palm olein-based polyols prepared using homogeneous (BF₃.Et₂O) and heterogeneous (K10 montmorillonite) catalysts in the ring-opening reaction of epoxidised palm olein (EPOo) were compared. Mono alcohols, i.e., methanol and isobutanol were selected as ring opening reagents. The formation of palm olein-based polyols was confirmed by the oxirane oxygen content (OOC), Fourier transformed infrared (FTIR) spectra and hydroxyl value (OHV) determinations. Based on the observation, the molecular weight (MW) of reagent used in the epoxide ring-opening reaction affected the viscosity of the obtained palm olein-based polyols. High oligomerisation was detected in palm olein-based polyol prepared using a homogeneous catalyst. The composition of hydroxyl monomer, dimer, trimer and tetramer in palm olein-based polyols were obtained from Gel Permeation Chromatography (GPC). Palm olein-based polyols prepared using heterogeneous catalyst exhibited the highest mono composition compared to other palm olein-based polyols. Heterogeneous catalyst provided palm olein-based polyols with low viscosity, less oligomerisation and functionality close to theoretical as compared to homogeneous catalyst. This finding can be used as a guideline in the synthesis of polyols with desired properties for targeted applications.