Vitrification of solid technological waste is currently under investigation. For this type of waste made up of metals, minerals, and organic matters, formulation studies were carried out in the NCAS (Na2O–CaO–Al2O3–SiO2) system in order to define a vitrifying additive to treat the entire waste deposit, while maximizing the waste loading. Main challenge related to this type of waste comes from the presence of alumina in very large quantities in the glass/glass–ceramics melt, enhancing the risk of melt solidification due to a fast and massive crystallization. Melt lock‐up can potentially occur at the operating temperature envisaged for the process (1400°C) and is prohibitive because it would lead to a premature stoppage of the process. The results obtained from casting tests, rheological experiments, and thermodynamic modeling enabled to provide an accurate estimation of the risk of melt lock‐up for NCAS compositions. It was highlighted that the composition had a major influence on the temperature at which massive crystallization might occur. From all the results obtained, the maximum Al2O3 content that could be incorporated in the final material was determined to be close to 50 wt%. The composition of a vitrifying additive was also statistically designed to treat the technological waste of interest.