A CoI2/(R)-BINAP, Zn, ZnI2, H2O system efficiently catalyzes the intermolecular asymmetric reductive coupling of alkynes with cyclic enones to afford highly regioand enantioselective β-alkenyl cyclic ketones. A possible mechanism that involves the formation of a cobaltacyclopentene intermediate from the alkyne and cyclic enone is proposed. © 2011 American Chemical Society.