The present invention provides a method for producing novel optically active diphosphine compounds �2,2'-bis(di-substituted phosphino)-1,1'-binaphthyl compounds! having a selectivity (chemoselectivity or enantioselectivity) and catalytic activity different from those of conventional BINAP compounds. In a method of the present invention for producing an optically active diphosphine compound (i.e., 2,2-bis(di-substituted phosphino)-1,1'-binaphthyl), 2,2'-bis(trifluoromethanesulfonyloxy)-1,1'-binaphthyl is reacted, in the presence of a transition metal-phosphine complex, with a phosphineoxide compound represented by the following general formula: A.sub.2 P(O)H wherein A represents a phenyl group; a mono- to tri-substituted phenyl group, wherein each substituent in the substituted phenyl group is individually selected from the group consisting of a halogen atom, a lower alkyl group, a lower alkoxy group or a lower halogenated-alkoxy group such that one or more of the substituents may be the same or different; a naphthyl group; a lower-alkyl naphthyl group; or a lower-alkoxy naphthyl group.