The chemical structure of a biolubricant plays an important role to determine its physicochemical and tribological properties. In this study, five triesters such as trimethylolpropane-triisostearate (T-IS), trimethylolpropane-triisooleate (T-IO), trimethylolpropane-trioleate (T-OA), glycerol-triisooleate (G-IO), and glycerol-trioleate (G-OA) have been synthesized via esterification of glycerol/trimethylolpropane with the respective free fatty acids (FFAs). FFAs such as methyl-branched isostearic and isooleic acids used for these T-IS, T-IO, and G-IO triester’s synthesis were previously made via skeletal isomerization of naturally derived oleic acid using a reusable zeolite catalyst. After esterification, any extra unreacted FFAs were recycled for the subsequent batch synthesis, resulting in little to no waste being produced. The chemical structures of the synthesized triesters have been determined with nuclear magnetic resonance, liquid chromatography-mass spectroscopy, Fourier transform infrared, and gas chromatography-mass spectroscopy. The physicochemical and tribological properties of these triesters have been compared to each other, and with that of high-oleic sunflower oil and polyalphaolefin, common lubricant base oils to demonstrate how the differences in molecular structure can influence their properties. Lubricant property analysis reveals that all the five synthesized triesters have the potential to be used as biolubricants. Practical application: modification in the chemical structure of natural lipids is found useful to improve their physicochemical and tribological properties and thus can be potentially used as biolubricants.This study offers a sustainable waste-free synthesis of triesters for potential use as biolubricants where renewable feedstock and reusable catalysts are used.