A new iron catalytic conjugate reduction of exocyclic α,β‐unsaturated carbonyl compounds with PMHS has been established for the first time. The reaction utilized PMHS as readily available, non‐toxic, and mild reductant that can be handled in open air. This protocol exhibits high compatibility with various substituents, and gives excellent yields, providing an environmentally benign and efficient access to construct synthetically useful α‐benzyl cyclic ketone scaffolds.