AbstractThe three‐dimensional microstructure of 8% yttria‐stabilized zirconia (YSZ) was measured by electron backscatter diffraction and focused ion beam serial sectioning. The relative grain boundary energies as a function of all five crystallographic grain boundary parameters were determined based on the assumption of thermodynamic equilibrium at the internal triple junctions. Grain boundaries with (100) orientations have low energies compared to boundaries of other orientations, and all [100] twist boundaries have relatively low energies. Other classes of boundaries with lower than average energies include [100] symmetric tilt boundaries with disorientations less than 40° and [111] twist boundaries with disorientations greater than 20°. At fixed misorientations, the relative areas of boundaries are inversely correlated to the relative grain boundary energy. The results suggest that texturing microstructures to increase the relative areas of [100] twist boundaries might increase the oxygen ion conductivity of YSZ ceramics.