Double axially chiral bisphosphorylimides have been used as catalysts in enantioselective Biginelli reactions. The three-component reaction of aromatic aldehydes, thiourea, and ethyl acetoacetate took place by using 5 mol-% catalyst in ethyl acetate at 50 °C. A series of chiral dihydropyrimidinethiones (DHPMs) were obtained in high yields (up to 97 %) with good to high enantioselectivities (up to 96 % ee) in only 12 hours.