Oxide-supported heterometallic complex structures were prepared by the impregnation of three different oxide supports with [Rh2Mo(eta(5)-C5Me5)(2)(S2C6H4)(2)(CO)(2)] through a CO exchange reaction with surface hydroxy groups. The original structural framework of the heterometallic complex with two Rh-Mo heterometal bonds was maintained on SiO2 and gamma-Al2O3, while the original complex structure was not maintained on TiO2; these structures were investigated by FT-IR, DR-UV-vis spectroscopy, and Mo/Rh K-edge EXAFS. Highly dispersed RhMo nanoclusters were obtained by heating the oxide-supported complexes in vacuum followed by treatment with H-2 at 773 K. The RhMo nanoclusters on TiO2 exhibited the highest activity for the oxidation of benzyl alcohol with O-2.