In aprotic solvents, Lewis basic F anion reduces Lewis acidic Ag(I) cation to Ag(0), forming metallic silver mirrors on the inner surfaces of reaction vessels and luminescent Ag-nanoparticles (AgNPs) in supernatant solutions, which emit blue light upon UV irradiation. The F-induced formation of silver mirrors and AgNPs was confirmed through X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), fluorescence spectroscopy, and mass spectrometry, whereas the Ag(I)-induced oxidation of F to gamma radical, followed by its conversion to HF2 via H-abstraction and H-bonding, was evident from F-19 NMR spectroscopy. This redox reaction is deactivated in water, as the reducing power of hydrated F diminishes drastically. Less Lewis basic Cl, Br, and I ions do not reduce Ag(I) to Ag(0), instead they can only form Ag(I) halide precipitates irrespective of protic or aprotic solvents. The Ag-coated surfaces, luminescent AgNPs, and ? radicals produced by this unprecedented redox reaction could be exploited as electrodes, light-emitting materials, and radical initiators, respectively.