Stereochemical control in the hydrogenation of alkynes with low-cost metal catalysts, an important technology in industry for the production of olefins that are central to the materials, food, pharmaceutical, and petrochemical arenas, has been a long-standing challenge. Here, we report on the E- and Z-selectivity in the hydrogenation of alkynes, controlled by two carbene ligands with cost-effective chromium catalysis. A cyclic (alkyl)(amino)carbene ligand that contain a phosphino anchor enables the hydrogenation of alkynes in a trans-addition manner, selectively formation of E-olefins. With an imino anchor-incorporated carbene ligand, the stereoselectivity can be turned, giving mainly Z-isomers. This ligand-enabled geometrical stereoinversion strategy by one metal catalysis overrides common methods in control of the E- and Z-selectivity with two different metal catalysis, allowing for highly efficient and on-demand access to both E- and Z-olefins in a stereo-complementary fashion. Mechanistic studies indicate that the different steric and electronic effect between these two carbene ligands may dominate the selective forming E- or Z-olefins in control of the stereochemistry.