The effect of the content of the hydrophobic agent in the cathode gas diffusion layer (GDL) on the mass transport in the proton exchange membrane fuel cells (PEMFCs) was studied using mercury porosimetry, scanning electron microscopy, and electrochemical polarization techniques. The mercury intrusion data and SEM micrograph indicated that the hydrophobic agent alters the surface and bulk structure of the GDL, thereby controlling gas-phase void volume and liquid water transport. The electrochemical polarization curves were measured and quantitatively analyzed to determine the oxygen transport limitation both in the catalyst layer and the GDL Evaluation of the parameter zeta, which represents the cathode GDL characteristics for liquid water transport, indicated that the optimized content of the hydrophobic agent and effective water management results from a trade-off between the hydrophobicity and the absolute permeability for faster water drainage. (C) 2009 Elsevier Ltd. All rights reserved.