[R,S;R,S]-Bis[2-[1-(dimethylamino)ethyl]ferrocenyl] dichalcogenides, (R,S)-{[EC 5 H 3 CHMe(NMe 2 )]Fe(C 5 H 5 )} 2 (E = S, Se, Te), act as chiral ligands for Rh(I)-catalyzed asymmetric transfer hydrogenation of alkyl aryl ketones using a diphenylsilane/methanol system to give the corresponding alcohols in fair to good yields with moderate enantiomeric excess (22-95% ee). The transfer of hydrogen from methanol to the resultant alcohol is confirmed by experiment using deuterated methanol (MeOD), and a new catalytic system containing Rh-hydride species is proposed. In the well-known 2-propanol/base system, the stereoselection is not satisfactory for Rh(I)-, Ir(I)- and Ru(II)-catalyzed reactions using these ligands.