A novel PtRu catalyst consisting of a Ru-rich core and a Pt-rich shell was synthesized using a two-step microwave irradiation technique. The synthesized PtRu/C catalysts were characterized by X-ray diffraction (XRD), extended X-ray absorption finestructure (EXAFS), transmission electron microscopy (TEM) as well as energy dispersive X-ray spectrometry (EDXS). The produced PtRu/C catalysts showed identical crystalline structure and diffraction peaks to Pt itself, but with negligible higher 2 shift degrees, indicating the formation of a specific composite structure rather than alloy formation. This novel structure of PtRu/C catalyst was also further verified via X-ray absorption spectroscopy. The particle size of PtRu catalysts identified by TEM was less than 5 nm. In order to investigate the CO tolerance in the hydrogen oxidation reaction (HOR). H(2) streams with six different concentrations of CO (0, 10, 50, 100, 300, and 500 ppm) were used. The electrocatalytic activity thus obtained was not only better than that of Pt/C catalyst in HOR, but also showed a better CO tolerance in various CO concentrations. Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.