Multilayer nanocomposite films composed of negative charged Ag nanosized particles and cationic polyallylamine hydrochloride (PAH) molecules were fabricated on polymer modified single-crystal silicon and flat glass slides by a layer-by-layer (LBL) molecular self-assembly technique. The X-ray photoelectron spectroscopy analysis showed that the formed Ag particles successfully absorbed onto the positively charged surfaces. The atomic force microscopy image of a two-cycle Ag/PAH bilayer film showed that no surface damage or defects existed on the thin-films surface. The Ag particles were densely and homogeneously distributed on the surface and relatively uniform in size. Goniometry was employed to verify the assembly process and the water contact angles oscillated regularly, depending on the composition of the outermost layer. By using the LBL deposition technique, a molecular-level ordered multilayer film with the thickness up to 40 layers (20 bilayers) was obtained. Results from UV-vis spectroscopy and ellipsometry measurements revealed that the self-assembly of the Ag/PAH multilayer film was well quantitative and reproducible. Thus we can conclude that the consecutive LBL deposition technique is a feasible and effective way to produce multilayer film and control the surface properties. (C) 2007 Elsevier B.V. All rights reserved.