Asymmetric hydrogenation catalyzed by transition metal complexes has been comprehensively studied. To reveal the mechanism of inducing the asymmetry, the complexes of his (dimethylglyoximato) cobalt and asymmetric amine are the most interesting because the intermediate complexes are easily isolated and crystallized. On the basis of the structure analyses of such complexes, we proposed that the asymmetry of the amine is transferred to the products at a transition state through the distortion of the his (dimethylglyoximato) cobalt moiety. This hypothesis was supported by the calculation of the potential energy at the transition state of which the structure was derived from the analysed ones.