The active electronic states of the supported metal catalysts (Ag, Cu, An) in the processes of alcohol partial oxidation were studied by the methods of IR spectroscopy of adsorbed CO, electron spectroscopy of diffuse reflectance, X-ray diffraction, XPS, EXAFS, ESR and electron microscopy. Comparison of the obtained catalytic and spectroscopic data revealed that one-charged cations M+ are the active sites of the local interaction on the metal catalyst surface in the processes of alcohol oxidation. The catalyst selectivity strongly depends on the effective charge of the surface active sites.