α‐Methylene‐γ‐butyrolactone is an important skeleton in many natural products and pharmaceuticals. The factors influencing the palladium‐catalyzed asymmetric synthesis of α‐chloromethylene‐γ‐butyrolactones were investigated, including ligands, additives, the chlorine source, temperature, and solvents. We found that the reaction had broad substrate scope for the synthesis of the corresponding chiral products when the ligand, chlorine source and additives were optimized. The results will improve the catalytic synthesis of chiral α‐chloromethylene‐γ‐butyrolactones. [ABSTRACT FROM AUTHOR]