Na deposition on the MnO(100) surface was investigated by temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS) and low energy electron diffraction (LEED). Na TPD and XPS results indicate that adsorbed Na interacts strongly with the MnO substrate to form an irreversibly-adsorbed, oxidic Na compound on the surface for coverages up to 1 monolayer (ML). This strongly-bound Na diffuses into the MnO subsurface and bulk at elevated temperatures above 500K. For Na coverages above 1 ML, metallic Na is present and desorbs from the surface below 500K. The deposition of Na on MnO(100) follows a Stranski–Krastanov (SK) growth mode, with the formation of metallic Na islands following completion of the first Na monolayer. After Na deposition, the surface exhibits a diffuse (1×1) LEED pattern, suggesting the formation of disordered Na overlayers. After heating to 1000K, the surface presents a (2×2) LEED pattern indicating that a surface reconstruction is induced by the diffusion of Na into the near surface region. CO2 can be used as a probe molecule in TPD to distinguish between metallic Na islands and oxidic Na in the first ML, and to indicate when Na that is still observable by XPS goes subsurface.