The experimental methods of X-ray and ultraviolet photoelectron spectroscopies (XPS and UPS, respectively) and the quantum mechanical calculations are applied for analysis of oxygen states on the silver oxide surface. At low temperatures (T < 470 K), the silver surface is intensively oxidized by a microwave oxygen discharge to form cuprite Ag2O. Two adsorbed oxygen species of the atomic (dissociative) and molecular (associative) nature can be adsorbed on the cuprite Ag2O surface. A comparison of the UPS data and the DFT calculations of molecular models Ag-2-O-2 and Ag-2-O-3 shows that the formation of ozonide-libe structures is preferable to that of peroxide species. Thermal stability and the reaction probability of the adsorbed states are investigated.