Enantioselective intramolecular [3 + 2] annulation of chalcones bearing an allene moiety has been successfully developed. The reaction was effectively promoted by amino acid-derived phosphines, in combination with achiral Brønsted acids. Dihydrocoumarin architectures were constructed in high yields and with excellent enantiomeric excesses. Theoretical studies via DFT calculations revealed that the hydrogen bonding network induced by achiral Brønsted acids/chiral phosphines could more efficiently distinguish between two enantioselective pathways, thus leading to enhanced enantioselectivity.