The fabrication of an electroactive nanostructured membrane (ENM) for oxygen reduction, made of layer-by-layer (LbL) films comprising Au nanoparticle-containing amine-terminated G4 PAMAM dendrimer alternated with poly(vinylsulfonic acid) (PVS) layers is reported. Electrochemical impedance spectroscopy and cyclic voltammetry show that electrodes with PVS/PAMAM-Au multiple bilayers are efficient for oxygen reduction and diffusion. A linear increase of oxygen reduction current occurs for up to 3 bilayers, with no further significant increase occurring for more than 3 bilayers. The 3-bilayer PVS/PAMAM-Au electrode, as an Au-ENM, is an attractive new system with potential for building diverse electrocatalytic devices with high molecular control. (c) 2007 Elsevier Ltd. All rights reserved.