Over the past years, transition metal-catalyzed enantioselective C-H activation has emerged as a powerful and efficient tool for the construction of molecular chirality. Significant progresses have been achieved on asymmetric C-H functionalization catalyzed by noble transition metals. From a practical and sustainable viewpoint, it would be highly appealing and desirable to explore the use of earth-abundant 3d transition metals as inexpensive and biologically friendly alternatives with complementary or even better reactivity and enantiocontrol. As an earth-abundant and inexpensive 3d transition metal, copper, was one of the prime contenders for this consideration. More importantly, owning to the easily accessible oxidation states ranging from 0 to +3 through both radical pathway and two-electron transfer, coppercomplexes might offer unique reactivity that are unavailable for precious metals. Significant advances have been achieved in Cu-catalyzed enantioselective C-H functionalization through outer-sphere mechanism, including asymmetric C(sp )-H insertion into copper carbenoid complexes with chiral Box ligand, atroposelective dimerization of electron rich arenes to construct axial chirality via SET mechanism, asymmetric Kharasch-Sosnovsky reaction, and hydrogen atom transfer radical relay mechanism involving the asymmetric reaction of the carboncentered radical with a chiral Cu center (Figure ). However, Cu-catalyzed asymmetric C-H activation by innersphere pathway, proceeding through the formation of an organometallic C-Cu intermediate, has scarcely been explored.