7.3-10 mol% yttria-doped zirconia (YDZ) was studied with emphasis on its long-term stability as solid electrolyte. The decomposition of common 8.5YDZ (950 °C) was detected by analytical TEM. As second issue, the microstructural and chemical properties of nanocrystalline 7.3YDZ thin films were investigated. Metastable t''-YDZ was found to precipitate in nanoscaled regions in YDZ up to 10 mol% yttria. Furthermore, a revised boundary of the c+t phase field, in which YDZ decomposes, is presented.