We report on the structural properties of epitaxial FeO layers grown by molecular beam epitaxy on MgO(111). The successful stabilization of polar FeO films as thick as 16 monolayers (ML), obtained by deposition and subsequent oxidation of single Fe layers, is presented. FeO/MgO(111) thin films were chemically and structurally characterized using low-energy electron diffraction, Auger electron spectroscopy and conversion electron Mössbauer spectroscopy (CEMS). Detailed in situ CEMS measurements as a function of the film thickness demonstrated a size-effect-induced evolution of the hyperfine parameters, with the thickest film exhibiting the bulk-wüstite hyperfine pattern. Ex situ CEMS investigation confirmed existence of magnetic ordering of the wüstite thin film phase at liquid nitrogen temperature.