This study compared the electro-oxidation of carbon monoxide adlayers formed on a codeposited and a layer-by-layer deposited Pt/Ru thin overlayer on a Au surface. Vertical arrays of smooth and nanoporous Au nanorods were used as a platform for the Pt/Ru overlayer-coating. The vertical arrays of Au nanorods served as high surface area templates, where the surface area could be controlled as a function of the rod length in a given geometrical surface area. A coating of the Au nanorod arrays with Pt/Ru via Cu underpotential deposition (UPD) steps allowed control of the overlayer thickness with an ultrathin film nature. The electronic modification of the Pt overlayer with a Ru underlayer became increasingly weaker with increasing Pt overlayer thickness. The thick Pt overlayer exhibited CO electro-oxidation that was similar to the electro-oxidation profile on the Pt bulk surface. Coating of the Au nanorod arrays with Pt/Ru through Cu UPD steps demonstrated an optimal electronic response between the Pt outer overlayer and the underlying Ru layer. It is expected that an ultrathin overlayer-coating strategy can be expanded to nanoporous Au nanorod arrays. These finding will facilitate better design of highly active Pt/Ru composite nanostructures for electrocatalysis. (c) 2007 Elsevier Ltd. All rights reserved.