AbstractFeaturing high levels of achievable oxygen non-stoichiometry δ, Ce_1−xZr_xO_2−δ solid solutions (CZO) are crucial for application as oxygen storage materials in, for example, automotive three-way catalytic converters (TWC). The use of CZO in form of films combined with simple manufacturing methods is beneficial in view of device miniaturization and reducing of TWC manufacturing costs. In this study, a comparative microstructural and electrochemical characterization of film and conventional bulk CZO is performed using X-ray diffractometry, scanning electron microscopy, and impedance spectroscopy. The films were composed of grains with dimensions of 100 nm or less, and the bulk samples had about 1 µm large grains. The electrical behavior of nanostructured films and coarse-grained bulk CZO (x > 0) was qualitatively similar at high temperatures and under reducing atmospheres. This is explained by dominating effect of Zr addition, which masks microstructural effects on electrical conductivity, enhances the reducibility, and favors strongly electronic conductivity of CZO at temperatures even 200 K lower than those for pure ceria. The nanostructured CeO₂ films had much higher electrical conductivity with different trends in dependence on temperature and reducing atmospheres than their bulk counterparts. For the latter, the conductivity was dominantly electronic, and microstructural effects were significant at T < 700 °C. Nanostructural peculiarities of CeO₂ films are assumed to induce their more pronounced ionic conduction at medium oxygen partial pressures and relatively low temperatures. The defect interactions in bulk and film CZO under reducing conditions are discussed in the framework of conventional defect models for ceria.