Alkaline earth metal aluminates activated by rare-earth ions (REn+) possess intensive luminescence upon UV excitation. The paper studies phase formation of calcium aluminate prepared by the sol-gel method. The stages of the end products’ formation using methods of the thermal and the infrared spectrometric analysis and X-ray diffraction are proposed. Dependence of phase composition, the surface morphology and luminescence properties on the annealing temperature of the precursor is investigated.