A facile and effective method is developed for the fabrication of ideal support and corresponding excellent catalysts. After spontaneous deposition of MnO2 onto electrospun carbon nanofibers (CNFs) in a solution of KMnO4 and subsequent thermal annealing, MnO-CNF hybrids with significantly enhanced graphitic structure and homogeneous surfaces defects are obtained. Further treatment with the solutions of H2PtCl6 and NaBH4 affords the resulting catalysts with codeposited Pt and MnO2 nanoparticles. To the best of our knowledge, it is the first time to simultaneously realize the combination of enhanced graphitization, uniform surface defects, and self N-doping of the carbon support materials. Compared to commercial Pt/XC72R and the counterparts without catalytic graphitization, Pt/MnO2-CNF exhibits significantly improved electrochemical active surface area, better CO tolerance for methanol electro-oxidation and excellent electrochemical durability. (C) 2014 Elsevier Ltd. All rights reserved.