The design and development of an extraordinarily interesting new class of chiral sulfur–olefin hybrid ligands with remarkable structural simplicity were described. These unique sulfinamide–olefin ligands have been proved to be highly effective ligands in rhodium-catalyzed asymmetric 1,4-addition reactions of aryl boronic acids to α,β-unsaturated carbonyl compounds (up to 99% yield and 98% ee).