Surface functionalization of Ag nanocubes and nanoparticles with catalytically active ruthenium carbonyl oligomers has been carried out successfully. These functionalized nanostructures catalyze hydrocarboxylation onto terminal alkynes at significantly enhanced rates (33 times) compare to those observed for free ruthenium oligomers. The rate enhancement is facilitated by adsorption of substrates on the surface of the nanoparticles, thus bringing them into close proximity with the catalyst. The size and shape of the Ag nanostructures were retained, indicating that the metallic cores act mainly as a docking site. (C) 2010 Elsevier Inc. All rights reserved.