Low‐basicity fluorine‐containing mold flux, which forms a porous slag film with NaF pores, is expected to solve the contradiction between heat transfer and lubrication in the continuous casting of peritectic steel. Herein, the kinetic mechanism and the influence of NaF gas formation based on the different fluorine raw materials (NaF, CaF2, and Na3AlF6) at 0.9 basicity and 6 wt% fluorine are investigated by the combination of experiments and calculations. The results show that CaF2 is the first to generate NaF gas at 1189 K, followed by Na3AlF6 (1238 K) and NaF (1328 K). NaF raw material produces the most NaF gas with the lowest activation energy in the three raw materials, due to high Na ion kinetic energy, the simple degree of polymerization, and Na‐F1 bonds. Correspondingly, NaF bubbles in the molten slag are the largest based on their aggregation. Na3AlF6 and CaF2 raw materials rank second and third, with F atoms primarily bonded as Al‐Fx and Ca‐Fx and the higher proportion of and structure. Notably, at 0.9 basicity and 6 wt% fluorine, Na3AlF6 as raw material generates a suitable amount of gas, making diffuse and fine NaF bubbles in the molten slag.