Ag+/ZSM-5 catalysts were prepared by an ion-exchange method. UV-irradiation of theAg+/ZSM-5 catalysts in the presence ofN2Oled to the photocatalytic decomposition ofN2OintoN2andO2at 298 K. Investigations of the effective wavelength of the irradiated UV-light for the reaction as well as the in-situ characterization of the catalysts by means of UV-Vis, photoluminescence and FT-IR spectroscopies revealed that the photoexcitation of theAg+−N2Ocomplexes formed between gaseousN2Oand the isolatedAg+ions exchanged within the zeolite cavities plays a significant role in the reaction.