A highly enantioselective intermolecular hydrophosphination reaction is described. The (Pigiphos)nickel (II)-catalyzed reaction of secondary phosphines and methacrylonitrile gives chiral 2-cyanopropy-lphosphines in good yield and high enantiomeric excess (ee's up to 94%; (R)-(S)-Pigiphos = bis{(R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethyl}cyclohexylphos phine). We propose a mechanism involving coordination of methacrylonitrile to the dicationic nickel catalyst followed by 1,4-addition of the phosphine, and then, rate-determining proton transfer. This mechanism is supported by (a) the experimentally determined rate law (rate = k'[Ni][methacrylonitrile][t-Bu2PH]), (b) a large primary deuterium isotope effect k(H)/k(D) = 4.6(1) for the addition of t-Bu2PH(D) at 28.3 degrees C in toluene-d(8), (c) the isolation and characterization of the species [Ni(kappa(3)-Pigiphos)(kappa N-methacrylonitrile)](2+), and (d) DFT calculations of model compounds.