Electrochemistry of oxides is an expanding area of oxide characterization. Although, interfacial characterization techniques including surface science methods have contributes substantially to our current understanding of the processes involved in the oxidation of metals and alloys. The characterization of subsurface zones and buried interfaces still remain a major challenge. Copper reactions with oxygen have been studied by high vacuum based techniques of AES, ELS, ISS, XPS. SIMS, LEED. STM, SEXAFS, HEIS and PFDMS and with optical methods, like UV-Vis-NIR, diffuse reflectance spectroscopy, FTIR and photoluminescence spectroscopes. However it has become evident that the processes that produce thermally and plasma grown oxide films on metals and alloys are electrochemical in nature and can be modeled by electrochemical concepts. Therefore, it is important that the oxide over layers, thin films and thick films be characterized by electrochemical means -with electrochemical methods, such as linear potential sweep voltammetry, cyclis voltammetry, galvanostatic reduction and coulometry which allow the identification of copper (I), copper (II) and copper (III) oxides. Interest in copper as a technologically important material needs to be met with greater understanding of the fundamental nature of copper oxide structures. In this study, the authors demonstrate the use of Linear Sweep Voltammetry (LSV) to study buried structures in the thermally grown oxide layers on copper. In particular, LSV can be used to detact reactions at buried interfaces. It also recognizes Cu3O2 and the decomposition of copper oxides at the metal-oxide layers on copper. In particular, LSV can be used to detect reactions at buried interface. The two key parameters that drive oxide growth and decomposition are demonstrated to be oxygen activity and the free energies of formation of the oxides. The complex nature of the oxidation of copper, as well as other metals and alloys, will be described qualitatively using the Modified Cabrera-Mott (C-M) Model. Surface studies of oxidation of metals and alloys need to be supported and complemented by other techniques such as electrochemical methods.