A highly regio- and enantioselective cobalt-catalyzed hydroboration/hydrogenation of internal alkynes with HBpin and a hydrogen balloon in one pot was developed. A new type of chiral imidazoline iminopyridine (IIP) ligand was introduced for the first time in this novel and efficient strategy. This protocol used relatively simple and available starting materials with good functional group tolerance to construct more valuable chiral secondary organoboronates. The primary mechanistic studies illustrated that the cobalt-catalyzed regioselective hydroboration of alkynes did initially occur followed by HBpin-promoted and cobalt-catalyzed enantioselective hydrogenation of alkenylboronates.