The acetylacetone precursor method was used to obtain powders of different ceria-based Ce(0.8)Ln(0.2)O(2-delta) (Ln = Y, Gd, Sm, La) compositions, and these powders were used to prepare disks which were sintered at 1150 degrees C after addition of Co nitrate, or at 1500 degrees C, without Co. These materials were characterized by impedance spectroscopy to distinguish the bulk and grain boundary behaviours. Arrhenius representations of bulk conductivity data show a gradual slope change, indicating defect interactions on cooling to intermediate and relatively low temperatures. Though data for different doped-ceria samples converge in the high temperature range, significant differences in conductivity and activation energy were found at low temperatures. The grain boundary behaviour shows dependence on the trivalent additive (Y, La, Gd or Sm), and the highest grain boundary conductivity for samples obtained without addition of cobalt nitrate was found for samples with La. However, addition of cobalt nitrate and sintering at relatively low temperature enhances the grain boundary conductivity of the remaining materials. The highest specific grain boundary conductivity was then found for samples containing Sm. Differences in grain boundary behaviour were interpreted based on differences in segregation of the rare earth additives for samples without Co-doping and preferential segregation of Co for Co-doped samples. (c) 2006 Elsevier Ltd. All rights reserved.