D2O adsorption to well-ordered Cu2O­(111) thin films has been explored with scanning tunneling microscopy, thermal desorption and infrared absorption spectroscopy. The molecules bind associatively to the oxide surface, whereby the first D2O layer experiences slightly stronger adhesion due to interfacial hydrogen bonds. At higher coverage, amorphous solid water (ASW) films condense on the Cu2O­(111) surface, as concluded from a dominant 155 K desorption peak and a broad vibrational band centered at 2540 cm–1. Development of ASW is also observed on bare Au(111), being used as substrate for Cu2O growth. In contrast to the oxide surface, no binding enhancement is detected for the D2O monolayer and desorption is accompanied by dewetting and transformation to crystalline ice. The different binding schemes of water reflect the hydrophilic versus hydrophobic character of Cu2O­(111) and Au(111) supports, respectively.