Ag nanoparticle films (simplified as nanofilms hereafter) on Si for electrochemical ATR surface enhanced IR absorption spectroscopy (ATR-SEIRAS) have been successfully fabricated by using chemical deposition, which incorporates initial embedding of Ag seeds on the reflecting plane of an ATR Si prism and subsequent chemical plating of conductive and SEIRA-active Ag nanofilms. Two alternative methods for embedding initial Ag seeds have been developed: one is based on self-assembly of Ag colloids on an aminosilanized Si surface, whereas the other the reduction of Ag+ in a HF-containing solution. A modified silver-mirror reaction was employed for further growth of Ag seeds into Ag nanofilm electrodes with a theoretically average thickness of 40-50 nm. Both Ag seeds and as-deposited Ag nanofilms display island structure morphologies facilitating SEIRA, as revealed by AFM imaging. The cyclic voltammetric feature of the as-prepared Ag nanofilm electrodes is close to that of a polycrystalline bulk Ag electrode. With thiocyanate as a surface probe, enhancement factors of ca. 50-80 were estimated for the as-deposited Ag nanofilms as compared to a mechanically polished Ag electrode in the conventional IRAS after reasonable calibration of surface roughness factor, incident angles, surface coverage, and polarization states. As a preliminary example for extended application, the pyridine adsorption configuration at an as-deposited Ag electrode was re-examined by ATR-SEIRAS. The results revealed that pyridine molecules are bound via N end to the Ag electrode with its ring plane perpendicular or slightly tilted to the local surface without rotating its C-2 axis about the surface normal, consistent with the conclusion drawn by SERS in the literature.