Protonated polyaniline (PANI) is directly polymerized on Nafion 117 (N117), forming a composite membrane, to act as a methanol-blocking layer to reduce the methanol crossover in the direct methanol fuel cell (DMFC), which is beneficial for the DMFC operating at high methanol concentration. The PANI layer grown on the N117 with a thickness of 100 nm has an electrical conductivity of 13.2 S cm(-1). The methanol permeability of the PANI/N117 membrane is reduced to 59% of that of the N117 alone, suggesting that the PANI/N117 can effectively reduce the methanol crossover in the DMFC. Comparison of membrane electrode-assemblies (MEA) using the conventional N117 and the newly developed PANI/N117 composite shows that the PANI/N117-based MEA outputs higher power at high methanol concentration, while the output power of the N117-based MEA is reduced at high methanol concentration due to the methanol crossover. The maximum power density of the PANI/N117-based MEA at 60 degrees C is 70 mW cm(-1) at 6M methanol solution, which is double the N117-based MEA at the same methanol concentration. The resistance of PANI/N117 composite membrane is reduced at elevated methanol concentration. due to the hydrogen bonding between methanol and PANI Pushes the polymer chains apart. It is concluded that the PANI/N117-based MEA performs well at elevated methanol concentration, which is suitable for the long-term operation of the DMFC. (C) 2009 Elsevier B.V. All rights reserved.