We compared the performance of the membrane electrode assembly for direct methanol fuel cells (DMFCs) composed of a pore-filling polymer electrolyte membrane (PF membrane) with that composed of a commercial Nafion-117 membrane. In DMFC tests, the methanol crossover flux was 23% lower in the PF membrane than in the Nafion-117 membrane even though the thickness of the PF membrane was 43% that of Nafion-117. This led to a higher DMFC performance and the lower overpotential of the cathode of the PF membrane. Feeding an aqueous 10M methanol solution at 50°C produced a low cathode overpotential, as low as 0.40V at 0.2 A in the PF membrane, whereas the potential was 0.65V at 0.2A in the Nafion-117 membrane. In contrast, the ohmic loss and anode overpotential were almost the same in the two membranes. We confirmed that a reduction in methanol crossover using the PF membrane results in lower cathode overpotential and higher DMFC performance. In addition, the electro-osmotic coefficient was estimated as 1.3 in the PF membrane and 2.6 in Nafion-117, based on a water mass-balance model and values showing that the PF membrane prevents the flooding of the cathode at a low gas flow rate using. A highly concentrated methanol solution can be applied as a fuel without decreasing DMFC performance using PF membranes.