Calcium–magnesium–alumina–silicate (CMAS) attack is a crucial issue for thermal–environmental barrier coatings (T/EBCs) with the ever-increasing operating temperature of turbine engines. In this study, CeO2 has been demonstrated as a promising protective material for T/EBCs against CMAS attack. At 1300 °C, CeO2 powder kept excellent phase and structural stability in molten CMAS; there were some CMAS constituents dissolved into the CeO2 lattice to form a solid solution. With higher CeO2 contents and longer duration time, more CeO2 solid solution particles were formed, which acted as the nucleating agent for CMAS crystallization. As a result, apatite, anorthite and wollastonite crystalline products were easily generated. At 1300 °C for 10 h, CeO2 pellets covered with CMAS powder had limited degradation, which was attributed to the rapid crystallization of molten CMAS due to the excellent nucleating agent effect of the precipitated CeO2 solid solution.