PtRu nanocatalyst supported on mesoporous carbon thin film (TFC) with incorporation of the non-metallic phosphorus is explored as an anodic catalytic material for direct methanol fuel cell (DMFC). The catalyst 20 wt.% PtRuP(0.1)/TFC gives a very high current density in the electrochemical oxidation of methanol, which is much enhanced than that of the PtRu/TFC without P loading and two times higher compared to a commercial PtRu/XC-72 catalyst. XPS and EXAFS analysis of the catalysts show that phosphorus helps to reduce the size of PtRu nanoalloy by acting as a surface protecting agent to the nanoparticles and it does not alter the electronic structure of PtRu. The PtRuP nanocatalyst with a particle size of 3 nm was found to have the best reactivity and catalytic stability. (C) 2010 Elsevier B.V. All rights reserved.