The complexes of various Rh precusors with ferrocenyl chiral ligand (R,S)-Cy2PF-PPh2 were found effective catalysts for the asymmetric hydroalkynylation reaction of norbornadiene derivatives. When RhCl3·3H2O was employed, good yields (up to 98%) and high enantioselectivities (up to >99.9% ee) could be obtained for the reactions of a broad scope of substrates.