A palladium-catalyzed asymmetric chlorocyclization of 1,6-enynes has been described. Controlling the chloride ion concentration in the system by substrate design is the key to achieving asymmetric chlorinated cyclization. In the presence of Pd(PhCN)2Cl2 and chiral phosphoramidite ligands, the reaction accesses diverse chiral (E)-α-chloromethylene-γ-butyrolactams with excellent E selectivity and enantioselectivity. The strategy features simple operations and mild conditions, offering a practical and reliable route for the synthesis of chiral butyrolactam compounds.