Simultaneous Synthesis of Chiral Medium‐Chain α‐Hydroxy Fatty Acid and ω‐Hydroxy Fatty Acid Using Enzymes/Whole Cell Cascade

α‐Hydroxy fatty acids and ω‐hydroxy fatty acids are highly versatile, value‐added chemicals widely utilized across various industrial sectors, including cosmetics, pharmaceuticals, and polymer production. Despite their significant utility, the chemical synthesis of α‐HFAs faces considerable challenges. These include the fact that the process is complex and environmentally hazardous, and it suffers from poor regioselectivity, frequently yielding nonspecific hydroxylation products. To address these limitations and promote sustainable chemical manufacturing, this study proposes and successfully demonstrates a novel, highly efficient, and green synthetic strategy utilizing enzymes and whole cell biocatalysts. The cascade initiates with the epoxidation of oleic acid’s double bond, a critical step that paves the way for further structural diversification. Following this enzymatic epoxidation, the cascade is completed using a whole‐cell biocatalyst designed to sequentially carry out epoxide hydrolysis by epoxide hydrolase, alcohol oxidation by secondary alcohol dehydrogenase, and the C─C bond cleavage and the generation of a hydroxy group by Baeyer–Villiger monooxygenase and lipase, which finally produced (2 R )‐2‐hydroxydecanoic acid and 8‐hydroxyoctanoic acid. This work establishes a robust, environmentally friendly, and highly modular platform for the chemoenzymatic simultaneous synthesis of valuable α‐hydroxy fatty acid and ω‐hydroxy fatty acid from abundant renewable resources.