Catalytic asymmetricPauson–Khandreactions with chiral bidentate phosphines as ligands have been successfully accomplished. The catalytic use of (S)-BINAP as a ligand was demonstrated to be the most effective in the cobalt-catalyzed reactions of 1,6-enynes, providing a facile entry to optically active 2-cyclopentenone derivatives with high enantioselectivity. A plausible mechanism for the asymmetric induction