A process for immobilizing metallic sodium in glass form. The process comprises: (A) introducing in a dispersed state, into a reactor, an amount of a vitrified matrix precursor, metallic sodium and iron oxide (Fe.sub.2O.sub.3) sufficient to ensure oxidation of the metallic sodium; (B) producing a homogeneous mixture of these constituents; (C) heating the mixture to a temperature between 1000 1600.degree. C. to form a molten homogeneous mixture in which the sodium introduced in (A) is converted to sodium oxide; and (D) recovering and cooling the molten mixture to obtain a vitrified matrix having a homogeneous composition, which matrix incorporates the sodium introduced in (A) as a constituent oxide. In a particular embodiment, the process may be used for the containment of metallic sodium containing radioactive elements.