A kinetic resolution of hindered Morita鈥揃aylis鈥揌illman adducts has been successfully achieved in excellent selectivities via Rh(I)-catalyzed asymmetric 1,4-addition/尾-hydroxyelimination with the use of a chiral sulfinamide/olefin hybrid ligand. This study provides a novel and efficient access to both optically active hindered highly functionalized alkenes and Morita鈥揃aylis鈥揌illman adducts.