Chiral coumarins and their derivatives are prominent bioactive structural units present in a wide range of natural products and pharmaceutical candidates. Therefore, the development of straightforward and efficient methodologies for the synthesis of readily functionalized chiral coumarins is of significant interest. Herein we report an enantioselective copper-catalyzed yne-allylic substitution of coumarins, resulting in a highly regioselective synthesis of diverse new classes of chiral coumarin derivatives with high efficiency and excellent functional group tolerance. Subsequent versatile transformations further demonstrate the substantial synthetic potential of this strategy in the field of biochemical research.