Self-assembled monolayers of diphenyldisulfide (DDS), naphthalenedisulfide (NDS), and diphenyldiselenide (DDSe) on polycrystalline silver films have been investigated by surface enhanced Raman spectroscopy (SERS) and X-ray photoelectron spectroscopy (XPS), DDS adsorbs on Ag through a homolytic cleavage of the S-S bond and resultant thiolate at the surface decomposes upon prolonged exposure to air. The geometry of the molecule is such that the benzene ring is almost horizontal to the surface. The Raman spectrum has been assigned in the light of ab-initio molecular orbital calculations. In DDSe, the Se-Se bond is retained upon adsorption and the molecule sticks up. In contrast, NDS is highly reactive on the microscopically rough surface so that a stable monolayer could not be prepared. A temperature dependent Raman study of the DDS monolayer shows the absence of any reorientation at the surface as one would expect from the adsorption geometry, XPS study complements the SERS data and shows the presence of Ag2S on an NDS exposed surface.