Interaction of water with an oxygenated Ag(111) surface leads to an enhancement of the surface restructuring and an activated formation of hydroxyl groups (OH) located stably on the surface and incorporated in the subsurface region, as evidenced by means of reflection electron microscopy (REM) and in situ Raman spectroscopy. Dehydroxylation of OHads at elevated temperatures releases the strongly bound oxygen species labelled O-gamma at the surface, and offers an alternative to the energetically less favorable pathway for the direct formation of the O-gamma species from molecular oxygen.