Cs2O–Al2O3 ceramic samples containing 20 and 33 mol % cesium oxide were prepared by сeramic technique and by the glycine–nitrate combustion process. The prepared samples were identified and characterized by X-ray powder diffraction and X-ray fluorescence analyses, scanning electron microscopy, and differential thermal analysis. X-ray powder diffraction and scanning electron microscopy showed that the phase composition and surface of the samples change significantly and nonmonotonically depending on the synthetic method used and the heat treatment parameters of the batch. Optimal synthetic conditions and heat treatment parameters for preparing Cs2O–Al2O3 samples were elucidated.