The total oxidation of toluene was investigated over TiO2-supported gold/iron catalysts prepared utilizing the [NEt4][AuFe4(CO)16] bimetallic carbonyl cluster salts. The catalysts have been characterized by means of infra-red spectroscopy (FT-IR), inductively coupled plasma spectrometry (ICP), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), total specific surface area (BET), X-ray photoelectron spectroscopy (XPS) and temperature programmed reduction (TPR) analyses. The novel preparation method resulted in iron oxide species finely and homogeneously distributed on the TiO2 and on small gold nanoparticles. The presence of gold has been found to enhance the selectivity of iron oxides towards the complete oxidation of toluene while the extent of the interaction between the two metals is important for catalytic activity.