The structure of the reactive cobalt complex catalyst for the enantioselective borohydride reduction of ketones was completely determined by ESI-MS, NMR, and X-ray analyses. It was confirmed that as an axial ligand, 1-chlorovinyl group derived from 1,1,1-trichloroethane was attached. Based on the X-ray analysis, two rotamers on cobalt-carbon bond were found in one unit. The obtained 1-chlorovinylcobalt(III) complex was examined for the enantioselective reduction to afford the reduced product in high yield with a high enantioselectivity.