Carbon aerogels exhibiting high Porous Volumes and high surface areas, differentiated by their pore-size distributions were used as Pt-supports in the cathode catalytic layer of H-2/air-fed PEM fuel cell. The cathodes were tested as 50 cm(2) membrane electrode assemblies (MEAs). The porous Structure of the synthesized catalytic layers was impacted by the nanostructure of the Pt-doped carbon aerogels (Pt/CAs). In this paper thus we present an experimental study aiming at establishing links between the porous structure of the cathode catalytic layers and the MEAs performances. For that purpose, the polarization curves of the MEAs were decomposed in 3 contributions: the kinetic loss, the ohmic loss and the mass-transport loss. We showed that the MEAs made with the different carbon aerogels had similar kinetic activities (low current density performance) but very different mass-transport voltage losses. It was found that the higher the pore-size of the initial carbon aerogel, the higher the mass-transport voltage losses. Supported by our porosimetry (N-2-adsorption and Hg-porosimetry) measurement, we interpret this apparent contradiction as the consequence of the more important Nafion penetration into the carbon aeorogel with larger pore-size. Indeed, the catalytic layers made from the larger pore-size carbon aerogel had lower porosities. We thus show in this work that carbon aerogels are materials with tailored nanostructured structure which can be used as model materials for experimentally testing the optimization of the PEM fuel cell catalytic layers. (C) 2009 Elsevier B.V. All rights reserved.