A simple, new type of chiral sulfinamide monophosphines, the so‐called Ming‐Phos ligands, is reported; these ligands could be easily prepared from inexpensive and commercially available starting materials. The Ming‐Phos ligands performed well in the enantioselective gold‐catalyzed cycloaddition reaction of 2‐(1‐alkynyl)‐alk‐2‐en‐1‐ones with nitrones. Both enantiomers of the products could be obtained in good yields and with excellent diastereo‐ and enantioselectivity through transformations that were catalyzed by gold complexes derived from two diastereomers of Ming‐Phos ligand M5 (Ar=1‐naphthyl). Ming‐Phos: A new type of simple chiral sulfinamide monophosphine ligands, the so‐called Ming‐Phos ligands, can be easily prepared from inexpensive and commercially available starting materials. The enantioselectivity of the reaction of yne–enones 1 with nitrones could be controlled by the diastereomeric ligands (R,RS)‐M5 and (S,RS)‐M5.