There is a worldwide interest in the development and commercialization of polymer electrolyte membrane fuel cells [PEMFCs] for vehicular and stationary applications. One of the major objectives is the reduction of loaded electrode materials, which is comprise of the Pt-based noble metals. In this paper, a novel chemical strategy is described for the preparation and characterization of carbon-supported and surface-alloys, which were prepared by using a successive reduction process. After preparing Au colloid nanoparticles, the supporting of Au colloid nanoparticles occurred spontaneously in the carbon black-dispersed aqueous solution. Then nano-scaled active materials were formed on the surface of carbon-supported Au nanoparticles. The structural and electrochemical analyses indicate that the active materials were deposited on the surface of Au nanoparticles selectively and that an alloying process occurred during the successive reducing process. The carbon-supported & surface-alloys showed the higher electrocatalytic activity than those of the particle-alloys and commercial one [Johnson-Matthey] for the reaction of methanol and formic acid oxidation. The increased electrocatalytic activity might be attributed to the effective surface structure of surface-alloys, which have a high utilization of active materials for the surface reaction of electrode.