Poly(vinyl alcohol) (PVA) nanofiber mats were collected on indium tin oxide (ITO) substrate by electrospinning method. A multilayer film composed of alpha-[P2W18O62](6-) (abbr. P2W18), a polyoxometallate (POM) anion, and poly(diallymethylammonium chloride) (abbr. PDDA) was fabricated by layer-by-layer (LBL) self-assembly technique on the PVA/ITO electrode. The PDDA/P2W18 multilayer film could be unselectively or selectively deposited on the PVA/ITO electrodevia changing the amount of PVA nanofibers on the ITO substrate. The scanning electron microscope (SEM) images showed that when the electrospun time was short the PDDA/P2W18 multilayer film was unselectively deposited on PVA nanofiber mats because the amount of PVA nanotibers was too little to cover most of the ITO substrate. However, when the electrospun time was long enough, the PDDA/P2W18 multilayer film was selectively deposited on PVA nanofiber mats because of the larger surface area and higher surface energy of PVA nanofibers in comparison with the flat ITO substrate. Growth process of the multilayer film was determined by cyclic voltammetry (CV). Electrocatalytic effects of the PDDA/P2W18 multilayer film unselectively and selectively deposited on the PVA/ITO electrode on NO2- were observed. (c) 2007 Elsevier Ltd. All rights reserved.