Nanocrystalline calcium and strontium singly doped ceria and co-doped ceria materials for solid electrolytes were prepared via a hydrothermal route. The effect of the hydrothermal treatment time on the solid solution composition was evaluated. Sr doped ceria was the most difficult to form, due to the Sr2+ large ionic radius. The small crystal size (12-16 nm) of powders allowed sintering into dense ceramic pellets at 1350 degrees C for 5 h. Raman spectroscopy evidenced a great lattice distortion for Sr doped and co-doped ceria materials, explaining the deterioration of the electrical properties for these ceramics. Besides that, a second phase was detected for Sr doped ceria pellet by using X-ray powder diffraction and Rietveld refinement of XRD data. Impedance measurements showed that Ca-doped ceria behaves as the best ionic conductor (sigma(g) 390 degrees C = 1.0 x 10(-3) S cm(-1)) since the nominal composition was achieved: on the other hand, Sr doped ceria performed as resistive materials since Sr incorporation into ceria lattice was critical. These results enhance the close interlace between electrical performance and chemical composition of alkaline earth doped ceria. (C) 2012 Elsevier B.V. All rights reserved.