The electrochemical double layer on Ag in alkaline NaCl solutions was examined ex situ with X-ray photoelectron spectroscopy (XPS). The specimens were removed from the electrolyte with hydrophobic surfaces and under potential control. The potential dependent surface concentrations of the adsorbed anions (Cl-, OH-), cations (Na+), the surface excess charge and the amount of adsorbed water were determined and compared to the results obtained for acidic NaCl solutions. The distinct differences found between both electrolytes were discussed in terms of a specific adsorption of hydroxide ions in the basic Cl--electrolyte; i.e., the OH--surface concentration has to be considered for a proper determination of the cationic excess charge and the potential of zero charge. In addition, the initial stages of silver (I) oxide formation were examined with XPS.