To alleviate the destructive alteration of the glass layer surface caused by gas evolution during the oxygen‐blocking process of the HfB2‐MoSi2‐SiC coating, CeO2 was incorporated to modify HfB2‐MoSi2‐SiC coating, and the anti‐oxidation mechanism at 1700°C in air was investigated. Compared with the unmodified HfB2‐MoSi2‐SiC coating, the addition of the refractory CeO2 to the Hf‐B‐Si‐O system leads to the formation of a stable Hf‐Ce‐B‐Si‐O complex phase glass, which substantially enhances the viscosity, stability, and self‐healing sealing properties of the glass layer. The introduction of 0.75 vol.% CeO2 significantly lowers the oxidative activity of the HfB2‐MoSi2‐SiC coating, boosting its average protective efficiency to 99.96% and reducing the maximal oxygen permeability by 43.48%, thus exhibiting superior oxygen‐blocking performance. However, excessive addition of CeO2 leads to an overabundance of oxygen release through its distinctive oxygen vacancy mechanism, which accelerates the formation of Hf‐oxides, resulting in excessive viscosity on the coating surface and leaving oxidation defects unrepaired.