The orientation of molecular H 2 O in a bilayer on defect-free NaCl͑100͒ and of chemisorbed OH adsorbed at F centers on the ͑100͒ surface of NaCl was investigated using angle-resolved O K edge near-edge x-rayabsorption fine-structure spectroscopy ͑NEXAFS͒. High-quality single crystalline thin films of NaCl͑100͒ of about four monolayers thickness were grown on Ge͑100͒. These films were bombarded with 250 eV electrons so that F and FЈ centers of a maximum density of about 10% of a monolayer were created. Whereas on the defect-free surface only molecular water is adsorbed, dissociation occurs at the F centers and OH Ϫ is bound. NEXAFS of molecular water shows almost no angular dependence even in the monolayer. This finding is consistent with formation of a hydrogen bonded bilayer of water suggested earlier. The OH species formed at the F centers is found to be inclined with respect to the surface normal by 39°Ϯ4°. An adsorption model is proposed.