Abstract: The multilayer films constructed from Dawson-type iron(Ⅲ)-monosubstituted tungstophosphate and a generation-4 poly(amidoamine) dendrimer(PAMAM) were prepared on the ITO electrode by the layer-by-layer self- assembly method and characterized by XPS, UV-Vis, CV and AFM. It was shown that P₂W₁₇Fe and PAMAM were gradually and uniformly incorporated into the films. Three couples of redox waves were observed in the cyclic voltammetry of the title multilayer films at acidic condition. The title multilayer films are stable and exhibit good electrocatalytic activity on the reduction of NO^-₂and BrO^-₃.