Ag nanoparticles were prepared by using the ion-exchange of Nafion combined with electrochemical reduction on the electrode. Ag nanoparticles are highly dispersed in Nafion film with an average size of 4.0 ± 0.2 nm. The amount of Ag nanoparticles can be readily controlled by the amount of Nafion coated on the electrode. Thus obtained Ag nanoparticles exhibit good catalytic activity for the reduction of H2O2 with a linear response to H2O2 in the concentration range of 0.04-8.0 mmol/L with a sensitivity of 0.34 μA/mmol/L and a detection limit of 1.0×10-8 mol/L.