The total oxidation of methanol and toluene, chosen as representative VOCs, was investigated over CeO2-supported Au/FeOx catalysts prepared utilizing the bimetallic carbonyl cluster salt [NEt4][AuFe4(CO)(16)]. Characterization data showed that the catalysts prepared by the reported method exhibit highly and homogeneously dispersed iron oxide species on the ceria support together with small gold nanoparticles, whose size increases on increasing the amount of gold/iron. Addition of iron oxide species did not substantially increase the methanol combustion activity of ceria, whereas the presence of the mixed gold and FeOx species has been found to strongly enhance the activity towards the total oxidation of methanol. In the case of the toluene combustion the addition of FeOx or FeOx/Au species caused a significant decrease in the activity of the bare CeO2. The above catalytic behavior was rationalized on the basis of different interactions occurring among gold, iron oxide and cerium oxide, which synergically affects both the reactivity of the surface oxygen and the capacity of the support to adsorb the organic reactant. (c) 2011 Elsevier B.V. All rights reserved.