We have investigated the adsorption of NO on a thin NiO (100) film of several layers thickness grown on top of a Ni (100) surface in comparison with data of an in vacuo cleaved NiO (100) single crystal. The layer exhibits a high defect density. We demonstrate via application of several surface-sensitive electron-spectroscopic techniques [ie, x-ray photoelectron spectroscopy (XPS), angle-resolved ultraviolet photoelectron spectroscopy (ARUPS), near-edge x-ray-absorption fine structure (NEXAFS), and high-resolution electron-energy-loss spectroscopy (HREELS)] that this layer has similar occupied (ARUPS) and unoccupied (NEXAFS) states as a bulk NiO (100) sample. In spite of its limited thickness, the band structure of the film exhibits dispersions perpendicular to the surface compatible with bulk NiO (100). It is shown that the electronic structure of the oxygen sublattice can be described in a band-structure picture while for the Ni sublattice electron localization effects lead to a breakdown of the band-structure picture. NO on NiO desorbs at 220 K. This indicates weak chemisorption. The NO coverage is close to 0.2 relative to the number of Ni surface atoms as determined by XPS.