Composite chitosan-phosphotungstic acid membranes were synthesized by ionotropic gelation. Their liquid uptake is higher for thin membranes (23 +/- 2 mu m), while it is lower (similar to 70%) for thicker membranes (50-70 mu m). Polarization curves recorded using single module fuel cell at 70 degrees C allowed to estimate a peak power density of 60 mW cm(-2)by using 1 M as methanol and low Pt and Pt/Ru loadings (0.5 and 3 mg cm(-2)) at the cathode and at the anode, respectively. Electrochemical impedance spectroscopy was used to estimate the membrane conductivity and to model the electrochemical behavior of methanol electrooxidation inside the fuel cell revealing a two-step mechanism mainly responsible of overall kinetic losses. Transport of methanol inside the membrane was studied by potentiostatic measurements, allowing to estimate a methanol diffusivity of 3.6 x 10(-6)cm(2)s(-1).