Nation membranes were modified by the in situ electrodeposition of polypyrrole inside the membrane pores and on the anode side only, in order to prevent the cross-over of methanol in the direct methanol fuel cell (DMFC). Pretreated Nafion membranes were first immersed in 0.1 M sulphuric acid containing the pyrrole monomer and subsequently removed from this solution and placed in a two-electrode solid-state electrochemical cell, where the polypyrrole was formed galvanostatically. The modified membranes were studied in terms of morphology, electrochemical characteristics and methanol permeability. FTIR and SEM confirmed the presence of the polypyrrole on the anode side of the Nafion membrane. SEM shows the polymer to be present both on the membrane surface and inside the membrane pores. It was found to be deposited as small grains, with two distinct sizes, the smallest particles have a diameter of around 100 nm, while the larger particles have diameters of around 700 nm. Methanol permeability was determined electrochemically and was shown to be effectively reduced. Cyclic voltammetry was performed in sulphuric acid, in pure methanol and in 50 vol.% methanol. The untreated Nation membrane showed CV curves which were similar in all electrolytes with electroactivity only at the extreme ends of the curve. The Nafion/Ppy membrane showed typical polypyrrole curves, with current densities lowest in sulphuric acid, and highest in the 50 vol.% methanol, respectively. For the methanol containing electrolytes, an additional oxidative peak appears in the CV, which may be related to electrocatalytic activity of the polypyrrole for methanol oxidation. (C) 2003 Elsevier B.V. All rights reserved.