In the present work, alumina-supported trimetallic Pd-Rh-Ru catalysts were synthesized and studied in comparison with the bimetallic Pd-Rh reference sample. The alloy nanoparticles were formed on the surface of the alumina support by thermolysis of the complex salts [Rh(NH3)5Cl][Pd(NO2)4] and [Rh(NH3)5Cl]0.5[Ru(NH3)5Cl]0.5[Pd(NO2)4], preliminary deposited via an incipient wet impregnation method. The influence of the conditions of the thermolysis process on the phase composition of the final products and the size of the trimetallic particles was established. Thus, nanoscale trimetallic (Rh-Ru-Pd) alloy particles of a given composition were obtained. The catalytic performance of the alumina-supported samples was examined in a CO oxidation reaction under prompt thermal aging conditions. It was ascertained that the addition of ruthenium only improves both the initial activity and thermal stability of the catalytic system. The state of each metal in the alloy nanoparticles was characterized by diffuse reflectance UV–vis spectroscopy and X-ray photoelectron spectroscopy.