Emerging technological knowledge is leading into new ventures. One such of these is the conversion of vegetable oils to polymers to augment the use of petroleum products as the source of polymeric raw materials. Vegetable oils, such as palm oil and soyabean oil, now mainly used in the food industry, could offer alternative applications for the industry. Recent works have studied new routes for the synthesis of polymers from natural oils. These polymers are considered excellent renewable sources of raw materials for the manufacture of polyurethane (PU) components with hydroxyl groups. In addition, the transformations of double bonds of triglycerides to hydroxyls and their application in PU have been the subject of many studies. The Malaysian Palm Oil Board (MPOB) started producing polyols from palm oil in the early 1990s. However, the early methods of preparing polyols from the vegetable oils suffer from certain drawbacks. The polyols were very viscous and of high acidity. The viscosity affects process parameters during production of PU foams and the acidity would influence the overall formulation’s performance. Furthermore, many conventional methods of preparing polyols from vegetable oils do not produce polyols having a significant content of hydroxyl groups and with desirable viscosity. After gaining two decades of experience, MPOB is now in a better position to offer improved versions of palm-based polyols and they are suitable for various applications in the PU industry. This article discusses MPOB’s experiences in the past decades in exploiting biopolyols from palm oil.