Catalysts that are derived from earth-abundant materials and display unique reactivity are of interest to the synthetic and the chemistry community as a whole. Although copper(I) hydride (CuH) was discovered in the 1840s and widely applied in organic synthesis since the 1980s, the potential of a catalytic system has not been fully realized. We have recently discovered that copper(I) hydride (CuH) complexes can undergo migratory insertion (hydrocupration) with relatively unactivated olefins. By intercepting the catalytically generated alkylcopper intermediates, a variety of useful bonds can be formed. A major focus has been the development of mild, enantioselective hydroamination of many types of olefins using N-electrophiles. We have also studied the use of CuH catalysts for C–C and C–X coupling, including in stereoselective addition to carbonyl derivatives. Our group is interested in the development and understanding of new catalysts and reagents that can broaden the scope and improve the efficiency of CuH-catalyzed asymmetric hydrofunctionalization reactions.