This study mechanistically investigated the pseudo-catalytic transesterification of oil-bearing biomass through a thermo-chemical pathway. As a case study, all experimental work was conducted with sesame seed and sesame oil. The pseudo-catalytic transesterification occurred in the presence of porous material (silica) since porous material provided reaction space as a micro reactor and drove the heterogeneous reactions between the mobile phase of methanol and the stationary phase of triglycerides (TGs) in sesame. The experimental work verified that the main driving force of pseudo-catalytic transesterification was temperature in the presence of porous material, which led to the direct derivatization of oil-bearing biomass into fatty acid methyl esters (FAMEs). Thermal cracking was observed at temperatures higher than 350 degrees C and the main experimental parameter initiating this thermal cracking was temperature and time. However, the optimal conditions identified in this study were temperatures lower than 350 degrees C, where the total yield of FAMEs reached up to 96.4 +/- 0.3% of lipid in sesame seed. The introduced technology would be applicable to the production of biodiesel and comprehensive lipid analysis in oil-bearing biomass. (C) 2016 Elsevier Ltd. All rights reserved.