A series of silica-supported Pt, Ru, and Pt-Ru catalysts has been synthesized using dendrimer-metal nanocomposite (DMN) precursors prepared by both co- and sequential complexation with metal salts. The catalysts have been characterized by several techniques, including electron microscopy, temperature-programmed titration of adsorbed oxygen, and X-ray diffraction. Liquid-phase selective hydrogenation of 3,4-epoxy-1-butene (EpB) was used as a probe reaction to evaluate their catalytic performance. The bimetallic catalyst prepared by the co-complexation method exhibits a superior catalytic activity Compared to the sequential one, and is much more active than a conventional catalyst prepared by incipient wetness. The activity enhancement is attributed to a bifunctional performance of the PtRu alloy sites created, based on a strong correlation between turnover frequencies, and both the alloy compositions and metal Surface site distributions. In addition, the co-complexation catalyst is selective toward crotonaldehyde, suggesting that this reaction pathway is favored on the PtRu sites. (C) 2009 Elsevier Inc. All rights reserved.