Abstract:H8‐BINOL‐derived phosphine‐oxazolines complexed with iridium were successfully applied for the asymmetric hydrogenation of the carbon‐carbon double bond of exocyclic α,β‐unsaturated carbonyl compounds. A valuable series of α‐chiral cyclic ketones, lactones, and lactams were therefore provided via the reaction in high yields and good to excellent enantioselectivity of up to 95 % ee. The effects of the ligands and substrate structures on the asymmetric catalysis were also discussed.