The crystallographic features of Gd-doped ceria were investigated at the operating temperature of solid oxides fuel cells, where these materials are used as solid electrolytes. (Ce1-xGdx)O2-x/2 samples (x = 0.1, 0.3, 0.5, 0.7) were prepared by coprecipitation of mixed oxalates, treated at 1473 K in air, and analyzed by synchrotron X-ray diffraction in the temperature range 673 K <= T <= 1073 K at the Elettra synchrotron radiation facility located in Trieste, Italy. In the whole temperature span a boundary was found at x similar to 0.2 between a CeO2-based solid solution (for x <= 0.2) and a structure where Gd2O3 microdomains grow within the CeO2 matrix, taking advantage of the similarity between Gd3+ and Ce4+ sizes; the existence of the boundary at x similar to 0.2 was confirmed also by measurements of ionic conductivity performed by impedance spectroscopy. Similar to what observed at room temperature, the trend of the cell parameter shows the presence of a maximum; with increasing temperature, the composition corresponding to the maximum moves toward lower Gd content. This evidence can be explained by analyzing the behavior of the coefficient of thermal expansion as a function of composition.