In this paper, silver nanoparticles (AgNPs), incorporated in the poly(perfluorosulfonic) acid membrane Nafion® 117, were fabricated by chemical reduction of the Ag+-loaded membranes, using HCOH in a basic medium as reducing agent. The AgNPs content within the membrane varied in proportion of the concentration of AgNO3 used in the incorporation step of Ag+ in the ion-exchange. Information on size and density of the AgNPs within the matrix was obtained by SEM analysis. The size of the AgNPs varied between 10 and 20 nm, regardless of the AgNO3 concentration used for their preparation, while AgNPs density was the higher, the greater was the AgNO3 concentration in the solution. Information on the oxidation state of Ag in the AgNPs and their distribution and aggregation on the surface of the Nafion membranes were obtained by SECM measurements. The use of [Ir(Cl)6]3- and Ru(NH3)63+ as redox mediators allowed establishing whether the AgNPs were interconnected to create nano-chain networks to provide AgNPs-loaded Nafion membranes with electronic conductivity. Moreover, combination of SECM and anodic stripping voltammetry allowed establishing the reactivity of the AgNPs-Nafion composites in terms of Ag(I) species released at the nanocomposite/solution interface. These aspects are relevant for the potential application of these AgNPs-loaded membranes for antimicrobial protection purposes