Polypyrrole films were deposited on stainless steel meshes by anodic electropolymerization of pyrrole dissolved in acetonitrile. Established on the electrochemical and morphological studies on the growth of polypyrrole film, both the oxidized, with PF6-, as counter-ion, and neutral polypyrrole membranes were obtained. The performances of these membranes towards ethanol-cyclohexane separation by pervaporation were investigated. Results indicate preferential permeation of ethanol and clearly show a feasibility of exploiting conducting polymers in the pervaporation process.