The main goal of this work was to study the formation of the luster effect in a glaze manufactured from a ceria-containing frit. The glazes obtained under industrial firing were studied using X-ray photoelectron spectroscopy, X-ray diffraction at room temperature and high temperature, and scanning electron microscopy with energy-dispersion spectroscopy. The mechanism of the luster effect on the surface was explained. The results indicated that the glaze presents iridescent colors on the surface, mainly associated with the formation of a very thin layer of CeO(2) crystals. Moreover, the CeO(2) crystals show a preferential orientation and different dimensions. The CeO(2) crystallization on the glaze was also studied using a hot-stage X-ray technique.