The novel organic-inorganic multilayer films containing poly(butanyl viologen) (abbreviated as PBV) and phosphomolybdic acid (H3PMo12O40, abbreviated as PMo12) have been fabricated on quartz slides, silicon wafers and glassy carbon electrode by the layer-by-layer self-assembly technique. The highly ordered multilayer films were characterized by the UV-visible spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray reflectometry (XRR), Atomic force microscopy (AFM) and cyclic voltammetry. UV-visible spectra revealed that the growth of the films for each deposition cycle was reproducible. FT-IR and XPS spectra confirmed the incorporation of PBV and PMo12 into the multilayer films. XRR revealed the film thickness at nanoscale, and AFM showed film surface with uniform and smooth morphology. In addition, the electrochemical behavior of the multilayer films at room temperature was investigated. As a result, the films presented good electrocatalytic activity toward BrO3-, H2O2 and NO2-, providing valuable information for exploring the potential applications in BrO3- sensors. (C) 2013 Elsevier B.V. All rights reserved.