The novel multifunctional thin films composed of transition metal complex tris(1,10-phenanthroline)ruthenium(II) Ru(phen)(3)Cl-2 (abbr Ru(phen)(3), phen = 1,10-phenanthroline), and Dawson-type polyoxometalate [P2Mo18O62](6-) (abbr P2Mo18) were fabricated on quartz, silicon and ITO substrates by layer-by-layer (LBL) method. The LBL films deposition were found to be linearly related to the number of bilayers as monitored by UV-vis spectroscopy. And the compositions of the films were measured by X-ray photoelectron spectra (XPS). The result of atomic force microscopy (AFM) revealed a relatively uniform surface morphology of the multilayer films. In particular, the films exhibited the photo-luminescence arising from pi*-t(2g) ligand-to-metal transition of Ru(phen)(3) and catalytic activity to the reduction of NO2- attributing to molybdenum-centered redox processes of P2Mo18. (c) 2006 Elsevier Ltd. All rights reserved.