A combination of in situ surface X-ray scattering (SXS) and cyclic voltammetry (CV) measurements have been performed to understand the structure and behavior of underpotentially deposited (UPD) Ag layers on Au(111) following transfer of the electrode to alkaline electrolyte (0.1 M KOH). UPD of Ag from 0.05 M H2SO4 + 1 mM Ag2SO4 electrolyte was used to form a monolayer and bilayer film of Ag on Au(111) before immersion into 0.1 M KOH electrolyte. Analysis of the SXS data shows that, while the bilayer Ag film is stable upon transfer to the alkaline electrolyte, the Ag monolayer film reorders to a partial bilayer structure upon or during the transfer process. The Ag-modified Au(111) electrode shows a potential response for OH– adsorption that is similar to that of Ag single crystal electrode surfaces.