We describe an approach for manipulation of biodegradable chitosan and poly(vinyl sulfonic acid) (PVS) in layer-by-layer (LBL) film adsorbed onto gold via ionic attraction. H2PtCl6 was deposited onto the LBL film, with chitosan/PVS layers serving as templates to yield metallic platinum. In electrochemical experiments this LBL film exhibited electrochemical stability, low permeability to methanol and conduction/diffusion of proton to maintain the electrolytic connection. The Pt/chitosan/PVS electrode also displayed electroreduction of molecular oxygen. With these features, this Pt/chitosan/PVS film may be used between the catalyst layer and the proton exchange membrane (PEM) in direct methanol fuel cells (DMFC) and biofuel cells. (c) 2005 Elsevier B.V. All rights reserved.