For Ag(I)-based photocatalysts, the photoreduction of Ag+ to metallic Ag is an unignorable issue, which is the major reason for their instability. If electrically neutral excitons rather than electrons were produced over Ag(I)-based photocatalysts, the photoreduction of Ag+ is expected to be greatly suppressed. To check this assumption, a Ag-based metal-organic framework containing pyrene, which is in favor of exciton production, is synthesized (denoted as Ag-PTS-BPY) and the structure is solved via single-crystal X-ray diffraction. Ag-PTS-BPY is applied in the photocatalytic selective oxidation of methyl phenyl sulfide, which displays high conversion and selectivity. As expected, no metallic Ag is formed after five cycles of reaction according to the results of X-ray diffraction, Fourier transform infrared, and X-ray photoelectron spectroscopy, and the high conversion is also maintained. The participation of excitons suppresses the involvement of electrons, which are believed to be the reason for the high stability of Ag-PTS-BPY.