Multicomponent oxide films are needed to meet the increasing demands of the electronics industry. Three main methods that involve oxidation of a metallic substrate are thermal, anodic and plasma oxidation. Today we do not have an adequate fundamental physical-chemical model of how multicomponent oxides evolve on alloys under these oxidizing conditions to design a wide range of materials for electronic devices. The three methods will be discussed in terms of physical/chemical parameters that influence the chemical nature and structure of the resulting oxides. By using surface studies of the oxidation behavior of numerous metals and alloys we have been able to delineate the factors which are most important to the oxide formation process and provide insight into the prediction of oxide layer structures. The electrochemical processes that occur during the materials reaction with a chosen environment will be used to discuss the physical and chemical mechanisms involved. Intrinsic and extrinsic electric fields will be shown to influence the chemical and structural nature of the resulting oxide structures. Examples will be presented from a number of metal and alloy systems that have been examined in our laboratory. These include Al, Ti, Zr, Nb, Mn, Cu and Ni and some of their selected alloys. The models that have developed from these studies are providing some predictive power in how the complex oxide overlayer will be chemically speciated and on its structure.