A high surface macroporous porous carbon (MPC) has been obtained by SiO2 nanoparticles template and further used as support for PtRu catalysts. MPC supported PtRu materials show an enhanced activity for methanol electrooxidation when compared with commercial catalysts. This observation is discussed in terms of reactant accessibility to active sites. The improved diffusion through the porous matrix influences not only methanol feeding, but also removal of reaction subproducts, as clearly shown by differential electrochemical mass spectrometry (DEMS). Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.