CeO2 films are technologically important as buffer layers for the integration of superconducting YBa2Cu3O7−δ films on {100}-biaxially textured Ni substrates, yielding a Ni–CeO2–YBa2Cu3O7−δ layer sequence. The Ni–CeO2 interface is a metal–oxide interface, and the misfit between substrate and film is about 9%. An epitaxial growth model was suggested for this system in the literature. The investigated films were deposited by a reactive thermal evaporation process at substrate temperatures of 650–670 °C with a thickness of 100 nm after deposition. The CeO2 films were characterized by plan-view and cross-section transmission electron microscopy, atomic force microscopy, and scanning electron microscopy. The CeO2 films had a strong {100} biaxial texture with a roughness of approximately 90 nm. No intermediate layer could be found by cross-section transmission electron microscopy at the Ni–CeO2 interface. The films had columnar grains with diameters of 20–50 nm, much smaller than the grain size of the Ni substrate, which was larger than 1 μm. Small-angle grain boundaries and small amounts of 〈111〉-oriented grains were evidenced in plan-view samples by diffraction patterns. The Moiré fringes technique was applied and was ideally suited to image the small rotations (≤3°) of the small CeO2 grains with respect to the Ni substrate. These small rotations of small grains showed that the growth was nonepitaxial, however, biaxially textured. In the CeO2 film samples, nanovoids 5–10 nm in size were observed and were mostly located close to the film surface. A model for the growth of CeO2 thin films on nickel substrates can be proposed on the basis of our results.