A novel method for the kinetic resolution of racemic secondary alcohols via their enantioselective benzoylation has been explored using CO, Ph3Bi(OAc)2, a catalytic amount of a chiral Pd(II) complex and AgOAc. In this catalytic system, Ph3Bi(OAc)2 has been revealed to work better than any other phenylating reagents such as PhB(OH)2 or PhSnMe3. It has also been disclosed that the planar chirality of optically active oxazolinylferrocenylphosphine (3e) has some positive effect on the enantioselectivity. Satisfactory enantioselectivity has not yet been obtained (up to 48% ee), but this reaction system seems to be interesting from the viewpoint of both asymmetric synthesis and organobismuth chemistry.