In order to improve the energy efficiency (fuel efficiency and electrical power) of direct methanol fuel cells (DMFCs), the hydrocarbon (HC) membrane-based membrane electrode assemblies (MEAs) are investigated under various operating conditions. The MEAs are then compared with the conventional Nafion-based MEA in terms of their efficiency and performance. The Faradaic efficiency and water transfer coefficient (WTC) are calculated based on mass balance measurements. The Faradaic efficiency of the HC-based MEAs is improved over the Nafion-based MEAs since methanol crossover decreased. The performance of HC-based MEAs shows strong dependency on the anode stoichiometry at high current densities probably because of the limited mass transport of fuel, which is not observed for the Nafion-based MEAs. The Nafion-based MEAs show a WTC of 3, whereas the HC-based MEAs show a very low WTC of -2, indicating the back-diffusion of water from the cathode to the anode. This may have limited mass transport by interrupting proton conduction at high current densities. The performance of HC-based MEAs at high current densities is improved as the fuel stoichiometry increases; High Faradaic efficiency is maintained by decreasing the cathode stoichiometry. (C) 2013 Elsevier Ltd. All rights reserved.