Electrospun poly (vinyl alcohol) (PVA) nanofibers mat was collected on indium tin oxide (ITO) substrate. Heat crosslinked nanofibers mat became water-insoluble and firmly fixed on ITO substrate even in water. Oppositely charged poly (allylamine hydrochloride) (PAH) and Dawson-type polyoxometalate (POM), Na 6 P 2 Mo 18 O 62 (P 2 Mo 18 ), were alternately assembled on PVA nanofibers-coated ITO substrate to construct multilayer film through an electrostatic layer-by-layer (LBL) technique. The scanning electron microscope (SEM) images showed that P 2 Mo 18 multilayer film was selectively deposited on PVA nanofibers while the unoccupied space by nanofibers on bare ITO was acted as substrate at the same time because the electrospun nanofibers have larger surface area and surface energy than the flat substrate. The cyclic voltammograms current responses of the P 2 Mo 18 multilayer film on PVA/ITO electrode showed three well-defined redox couples of P 2 Mo 18 , but very small because P 2 Mo 18 multilayer film was selectively deposited on PVA nanofibers with poor conductivity. In addition, the photochromic behavior of P 2 Mo 18 multilayer film on PVA/ITO was investigated through UV–vis spectra and electron spin resonance (ESR). Fourier-transform infrared (FT–IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) proved that the charge-transfer complex was formed between PAH and P 2 Mo 18 after UV irradiation.