Thin films of cerium dioxide (CeO2) were deposited by atomic layer deposition (ALD) at 250 {\deg}C on both Si and TiN substrates. The ALD growth produces CeO2 films with polycrystalline cubic phase on both substrates. However, the films show a preferential orientation along <200> crystallographic direction for CeO2/Si or <111> for CeO2/TiN, as revealed by X-ray diffraction. Additionally, CeO2 films differ in interface roughness depending on the substrate. Furthermore, the relative concentration of Ce3+ is 22.0% in CeO2/Si and around 18% in CeO2/TiN, as obtained by X-ray photoelectron spectroscopy (XPS). Such values indicate a ~10% off-stoichiometry and are indicative of the presence of oxygen vacancies in the films. Nonetheless, CeO2 bandgap energy and refractive index at 550 nm are 3.54+/-0.63 eV and 2.3 for CeO2/Si, and 3.63+/-0.18 eV and 2.4 for CeO2/TiN, respectively. Our results extend the knowledge on the structural and chemical properties of ALD-deposited CeO2 either on Si or TiN substrates, underlying films differences and similarities, thus contributing to boost the use of CeO2 through ALD deposition as foreseen in a wide number of applications.