A facile strategy has been developed for the preparation of bimetallic gold-silver (Au-Ag) nanocomposite films by alternating absorption of poly-(ethyleneimine)-silver ions and Au onto substrates and subsequent reduction of the silver ions. The composition, micro-structure and properties of the {PEI-Ag/Au}(n) nanocomposite films were characterized by ultraviolet visible spectroscopy (UV-vis), transmisson electron microscopy (TEM), field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), surface enhanced Raman scattering (SERS) and cyclic voltammetry (CV). The UV-vis characteristic absorbances of {PEI-Ag/Au}(n) nanocomposite thin film increase almost linear with the number of bilayers, which indicates a process of uniform assembling. Appearance of a double plasmon bands in the visible region and the lack of apparent core-shell structures in the TEM images confirm the formation of bimetallic Au-Ag nanoparticles. The result of XPS also demonstrates the existence of Ag and Au nanoparticles in the nanocomposite films. TEM and FESEM images show that these Ag and Au nanoparticles in the films possess sphere structure with the size of 20-25 nm. The resulting {PEI-Ag/Au}(n) films inherit the properties from both the metal Ag and Au, which exhibits a unique performance in SERS and electrocatalytic activities to the oxidation of dopamine. As a result, the {PEI-Ag/Au}(n) films are more attractive compared to {PEI-Ag/PSS}(n) and {PEI/Au}(n) films. (C) 2012 Elsevier B.V. All rights reserved.