We characterize electrical conductivity, microstructure, nano-scale grain boundary structure and chemistry of ceria electrolytes with nominal compositions of Gd0.2Ce0.8O2-delta (GDC) and Gd0.11Pr0.04Ce0.85O2-delta (GPDC).The electrolytes are fabricated using mixed oxide nanopowders synthesized by spray drying. AC impedance spectroscopy was performed from 150 degrees C to 700 degrees C in air to determine grain-interior electrical conductivity. Grain-boundary conductivity was determined below 300 degrees C. The grain-interior conductivity of the GPDC was higher than that of GDC by as much as 10 times, depending on the temperature. The GPDC specific grain-boundary conductivity was measured to be approximately 100 times higher than that of GDC. Energy dispersive X-ray spectroscopy (EDX) and electron energy-loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM) confirmed the grain-to-grain compositional uniformity of both materials following heat treatments. Grain boundaries were free of glassy intergranular phases; dopant concentration and Ce oxidation state were found to vary significantly near grain boundaries. Boundary core composition was estimated from STEM EELS to be Gd0.62Ce0.38O2-delta, and Gd0.29Pr0.16Ce0.55O2-delta in GDC and GPDC, respectively. Pr segregation to grain boundaries in the GPDC is hypothesized to enhance conductivity by both decreasing oxygen vacancy migration energy, and inducing mixed ionic-electronic conductivity in the near-boundary region. (C) 2014 Elsevier B.V. All rights reserved.