Rational design and controlled preparation of highly effective catalysts towards the preferential oxidation of CO have significant importance for the utilization of hydrogen energy. In this work, PtFe/C bimetallic catalysts have been successfully prepared by a one-pot surfactant-free polyol process, where Pt metal nanoparticles serve as catalysts to reduce Fe ions to metallic form on the surface. The resulting PtFe/C catalysts are investigated for a PROX CO reaction and characterized by ICP-AES, XPS, XRD, TEM, HS-LEIS. It is found that PtFe/C with an optimal Fe loading shows extremely high activity and stability. These characterization results reveal that PtFe/C adopts a structure of Fe rich surface and Pt dominated cores. The excellent catalytic performances over PtFe/C catalysts are attributed to the efficient activation of O-2 by Fe species located on the catalyst surface, indicated by the results of CO and O-2 pulse experiments. Additionally, other PtM/C (M = Cu, Ni) catalysts possessing the similar structure with that of PtFe/C can also be synthesized using the established one-pot surfactant-free polyol process. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.