Often there are only subtle parameters which separate the chemical interaction or structure of compounds which impede or inhibit atmospheric corrosion and those which initiate of accelerate it. The properties, both physical and chemical, required (1) for an effective vapor phase corrosion inhibitor (VCI) are very critical. This has resulted in severely limiting the number of such compounds presently available on a commercial basis (2). The exact nature of the specific bonding between the metal and the inhibitor is not precisely known nor are the effects of surface contaminants and normal surface chemistry well established. The following work represents investigations involving studies of the VCI/metal interfacial bonding and how surface chemistry affects this chemistry. The capabilities of modern, sophisticated analytical instruments including ESCA (XPS), SIMS, and ISS have greatly enhanced the ability to obtain such detailed information. These techniques have been utilized extensively in the following investigations of VCI interactions with Fe, Al, and Cu metals.