Electrical characterization of 10 mol% gadolinia doped ceria (CGO10) films of different thickness prepared on MgO (100) substrates by pulsed laser deposition is presented. Dense polycrystalline and textured films characterized by fine grains (grain sizes <18 nm and <64 nm for a 20-nm and a 435-nm film, respectively) are obtained in the deposition process. Grain growth is observed under thermal cycling between 300-800°C, as indicated by X-ray based grain-size analysis. However, the conductivity is insensitive to this microstructural evolution but is found to be dependent on the sample thickness. The conductivity of the nanocrystalline films is lower (7.0 × 10 −4 S/cm for the 20-nm film and 3.6 × 10 −3 S/cm for the 435-nm film, both at 500°C) than that of microcrystalline, bulk samples (6 × 10 −3 S/cm at 500°C). The activation energy for the conduction is found to be 0.83 eV for the bulk material, while values of 1.06 eV and 0.80 eV are obtained for the 20 nm film and 435 nm film, respectively. The study shows that the ionic conductivity prevails in a broad range of oxygen partial pressure, for example down to about 10 −26 atm at 500°C.