Enantioselective Cu-catalyzed conjugate addition of organometallic reagents to Michael acceptors is one of the most trailblazing and powerful method in organic chemistry to acquire enantioenriched β-substituted natural or unnatural adducts through C-C bond formation. Although numerous research results have been published with α,β-unsaturated compounds such as carbonyl derivatives, sulfones, nitroalkenes, and nitroenynes to date, a wide range of discoveries in this field is still to be made. However, in order to synthesize new families of compounds and complex synthons at the same time, new asymmetric organic reactions or methodologies with more sensitive substrates must be investigated. The interest in the development of new synthetic methodologies with more challenging substrates is related to the preparation of natural and unnatural adducts through a direct access of a large variety of important chiral compounds from the same starting material. To achieve this purpose, we investigated a new copper-catalyzed asymmetric conjugate addition with various organometallic reagents to functionalized α,β-unsaturated aldehydes and β,γ-unsatured-α-ketoester.