The reaction of Ru-5(CO)(15)(mu(5)-C) with Ni(COD)(2) in acetonitrile at 80 degrees C affords the bimetallic octahedral ruthenium-nickel cluster complex Ru5Ni(NCMe)(CO)(15)(mu(6)-C), 3. The acetonitrile ligand in 3 can be replaced by CO and NH3 to yield Ru5Ni(CO)(16)(mu(6)-C), 4, and Ru5Ni(NH3)(CO)(15)(mu(6)-C), 5, respectively. Photolysis of compound 3 in benzene and toluene solvent yielded the eta(6)-coordinated benzene and toluene Ru5Ni carbido cluster complexes Ru5Ni(CO)(13)(eta(6)-C6H6)(mu(6)-C), 6, and Ru5Ni(CO)(13)(eta(6)-C7H5)(mu(6)-C), 7, respectively. All five new compounds were structurally characterized by single-crystal X-ray diffraction analyses.