Ag+/ZSM-5 catalyst was prepared by an ion-exchange method. In situ EXAFS, ESR, photoluminescence, and diffuse reflectance (DR) spectroscopy were applied to characterize the Ag+/ZSM-5 catalyst. UV irradiation of the Ag+/ZSM-5 catalyst in the presence of NO led to the photocatalytic conversion of NO into N-2, N2O and NO2 at temperatures as low as 298 K. The wavelengths of the effective UV irradiation were determined. The results obtained in this study suggest that electron transfer from excited Ag+ ion into the pi anti-bonding molecular orbital of NO plays a significant role in the photocatalytic decomposition of NO.