AbstractThe capillary condensation is affected by micropore and nanopore of catalyst layer on fuel cell. Due to limitation of sluggish mass transport and electrocatalytic activity, to retain the pore skeleton of carbon and metal nanoparticles are very significant for enhanced utilizations of pore structure in electrochemical reaction. Besides, thickness of electrocatalyst layer is very crucial due to one of the factor affected by cell performance of direct methanol fuel cell. Highly loaded four Pt−Ru anode catalysts supported on resorcinol‐formaldehyde (RF) polymer based on meso‐porous carbons (80 wt.% Pt−Ru/carbon cryogel, 80 wt.% Pt−Ru/carbon xerogel and 80 wt.% Pt−Ru/carbon aerogel) and conventional carbon (80 wt.% Pt−Ru/Vulcan XC‐72) were prepared by colloidal method for direct methanol fuel cell. These catalysts were characterized by X‐Ray diffraction (XRD), High resolution transmission electron microscopy (HR‐TEM) and X‐ray photoemission (XPS). The results of CO stripping voltammetry, cyclic voltammetry (CV) and single cell test performed on DMFC show that Pt−Ru/carbon cryogel and Pt−Ru/carbon aerogel exhibits better performances in comparison to Pt−Ru/carbon xerogel and Pt−Ru/Vulcan XC‐72. It is thus considered that particle size, oxidation state of metal and electrochemical active surface area of these catalysts are important role in electrocatalytic activity in DMFC.