The impact of nanoarchitecture on the electrical properties of sol-gel-derived Ce0.9Gd0.1O2 (CGO) is evaluated in O-2 from 350 to 600 degrees C. The high degree of interconnectivity established between the < 10 nm crystallites in CGO aerogels (see figure) yields an electroceramic that responds as though it contains no grain boundaries and which exhibits long-range pathways for ionic diffusion (ca. 0.5 mm).