Gd3+ doped Ce oxides are a major candidate for use as the electrolyte in solid oxide fuel cells operating at ∼500 °C. Here, the effect of the atomic structure on the local electronic properties, i.e. oxygen coordination and cation valence, at grain boundaries in the fluorite structured Gd0.2Ce0.8O2-x ceramic electrolyte is investigated by a combination of atomic resolution Z-contrast imaging and electron energy loss spectroscopy (EELS) in the scanning transmission electron microscope (STEM). In particular, EELS analyses from grain boundaries reveals a complex interaction between segregation of the dopant (Gd3+), oxygen vacancies and the valence state of Ce. These results are similar to observations from fluorite-structured Yttria-Stabilized Zirconium (YSZ) bicrystal grain boundaries.