A composite multilayer film constructed of Dawson anion [P2Mo18O62](6-) and diazo resin (DR) was prepared by the electrostatic layer-by-layer (LbL) self-assembly method. The film could be stabilized by the photoinduced interaction between Dawson anion and diazo resin. IR spectra and X-ray photoelectron spectra revealed the possible occurrence of partial transformation from electrostatic interaction to covalent interaction between layers of the film after irradiation by UV light. Such transformation evidently increases the endurance of the film, which was demonstrated by AFM images and etching experiments with organic solvent. This study provides a new route to stabilze the polyoxometalate-based multilayer film by virtue of the photoinduced reaction with photosensitive polymer. (C) 2004 Published by Elsevier B.V.