Nanocrystalline powders of CGO materials with different contents of Gd were prepared by a freeze-drying method and used to prepare dense ceramic samples. This method allowed one to obtain good quality samples to re-examine the reducibility of CGO materials. These materials were characterized by a combination of coulometric titration, impedance spectroscopy and ion blocking measurements to evaluate changes in point defect chemistry and mixed conducting properties. We have examined the onset of n-type conductivity as a function of temperature and oxygen partial pressure, and this information was used to re-examine the mixed transport properties in reducing conditions imposed by fuels, and also the OCV obtained with CGO solid electrolyte cells under air/CGO/fuel gradients. The polaron mobility was also evaluated and was found to depend slightly on temperature and to decrease with increasing oxygen deficiency. This confirmed that the electronic conductivity is mainly dependent on reducibility. (C) 2007 Elsevier B.V. All rights reserved.