AbstractThe mature manufacturing of synthetic lubricants (poly‐α‐olefins, PAO) proceeds through oligomerization, polymerization, and hydrogenation reactions of petrochemical ethylene. In this work, we utilize the inexpensive bio‐derived oleic acid as raw material to synthesize a crotch‐type C45 biolubricant base oil via a full‐carbon chain synthesis without carbon loss. It contains several cascade chemical processes: oxidation of oleic acid to azelaic acid (further esterification to dimethyl azelate) and nonanoic acid (both C9 chains). The latter is then selectively hydrogenated to nonanol and brominated to the bromo‐Grignard reagent. In a next step, a C45 biolubricant base oil is formed by nucleophilic addition (NPA) of excessive C9 bromo‐Grignard reagent with dimethyl azelate, followed by subsequent hydrodeoxygenation. The specific properties of the prepared biolubricant base oil are almost equivalent to those of the commercial lubricant PAO6 (ExxonMobil). This process provides a new promising route for the production of value‐added biolubricant base oils.