The thermal and photochemical characteristics of silver 4-nitrobenzoate (Ag-4NBA) was investigated using various analytical tools, such as X-ray diffraction (XRD), diffuse reflectance infrared Fourier transform electron spectroscopy, Raman spectroscopy, thermogravimetric analysis, scanning electron microscopy, and transmission electron microscopy. Because the organic moieties anchored on the Ag nanoparticles can be completely removed by heating to 750 K or higher, optically tunable, surface-enhanced Raman scattering (SERS)-active Ag films can be reproducibly fabricated on glass microscope slides.