Intense research efforts are directed toward Cu and Cu2O based catalysts as they are viewed as potential replacements for noble metal catalysts. However, applications are hampered by deactivation, e.g., through facile complete oxidation to CuO. Despite the importance of the redox processes for Cu2O catalysts, a molecular level understanding of the deactivation process is still lacking. Here we study the initial stages of oxidization of well-defined Cu2O bulk single crystals of (100) and (111) termination by means of synchrotron radiation X-ray photoemission spectroscopy (XPS) and scanning tunneling microscopy (STM). Exposure of the (100) surface to 1 mbar O-2 at 25 degrees C results in the formation of a 1.0 monolayer (ML) CuO surface oxide. The surface is covered by 0.7 ML OH groups from trace moisture in the reaction gas. In contrast, neither hydroxylation nor oxidation was observed on the (111) surface under similar mild exposure conditions. On Cu2O(111) the initial formation of CuO requires annealing to similar to 400 degrees C in 1 mbar 02, highlighting the markedly different reactivity of the two Cu2O surfaces. Annealing of the (100) surface, under ultrahigh vacuum conditions, to temperatures up to similar to 225 degrees C resulted in removal of the OH groups (0.46 ML decrease) at a rate similar to a detected increase in CuO coverage (0.45 ML increase), suggesting the reaction path 2OH(adsorbed) + CU2Osolid -> H2Ogas + 2CuO(solid). STM was used to correlate the observed changes in surface chemistry with surface morphology, confirming the surface hydroxylation and CuO formation. The STM analysis showed dramatic changes in surface morphology demonstrating a high mobility of the active species under reaction conditions.