The zwitterion-coated polyamidoamine (ZC-PAMAM) dendrimer with ammonium and sulfonic acid groups has been synthesized and used as filler for the preparation of PBI-based composite membranes for direct methanol fuel cells. Polybenzimidazole (PBI)/ZC-PAMAM dendrimer composite membranes were prepared by casting a solution of PBI and ZC-PAMAM dendrimer, and then evaporating the solvent. The presence of ZC-PAMAM dendrimer was confirmed by FT-IR and energy-dispersive X-ray spectroscopy (EDS) mapping of sulfur and oxygen elements. The water uptake, swelling degree, proton conductivity, and methanol permeability of the membranes increased with the ZC-PAMAM dendrimer content. For the PBI/ZC-PAMAM-20 membrane with 20 wt% of ZC-PAMAM, it shows a proton conductivity of 1.83 x 10(-2) S/cm at 80 degrees C and a methanol permeability of 5.23 x 10(-8) cm(2) s(-1). Consequently, the PBI/ZC-PAMAM-20 demonstrates a maximum power density of 26.64 mW cm(-2) in a single cell test, which was about 2-fold higher than Nafion-117 membrane under the same conditions. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.