Through the layer-by-layer technology, (Pd/dcbp)(n) (dcbp=4,4'-dicyanobiphenyl) multilayer films were prepared by alternately immersing quartz slide pre-coated with poly(ethylenimine) layer in PdCl2 and dcbp aqueous solutions. (Pd/dcbp)(n) multilayers were characterized by UV-vis spectra, atomic force image and X-ray photoelectron spectroscopy (XPS). UV-vis spectra showed that the fabrication of (Pd/dcbp)(n) multilayers depends on the coordination interaction between palladium ions and C N moieties. The results of XPS analysis show that mixed zero-valent and divalent Pd coexist in (Pd/cbp)(n) multilayers. During the self-assembly process, Pd ions within the multilayers are in situ reduced by weak reducibility of the ligand bpcn. Transmission electron microscopy further demonstrated that Pd nanoparticles within multilayers were highly dispersed and uniform. The electrode modified with Pd/dcbp multilayer films showed electrocatalytic activity toward methanol oxidation in alkaline medium. (C) 2012 Elsevier B. V. All rights reserved.