Multi-walled carbon nanotubes (MWCNT)/polyelectrolyte (PE) hybrid thin films were fabricated by alternatively depositing negatively charged MWCNT and positively charged (diallyldimethylammonium chloride) (PDDA) via layer-by-layer (LbL) assembly technique. The stepwise growth of the multilayer films of MWCNT and PDDA was characterized by UV-vis spectroscopy. Scanning electron microscopy (SEM) images indicated that the MWCNT were uniformly embedded in the film to form a network and the coverage density of MWCNT increased with layer number. Au nanoparticles (NPs) could be further adsorbed onto the film to form PE/MWCNT/Au NPs composite films. The electron transfer behaviour of multilayer films with different compositions were studied by cyclic voltammetry using [Fe(CN)(6)](3-/4-) as an electrochemical probe. The results indicated that the incorporation of MWCNT and Au NPs not only greatly improved the electronic conductivity of pure polyelectrolyte films, but also provided excellent electrocatalytic activity towards the oxidation of nitric oxide (C) 2011 Elsevier Ltd. All rights reserved.