As an essential synthetic material used in continuous casting of steels, mold fluxes improve the surface quality of steel slabs. In this study, a CaO-SiO₂-Na₂O based low-fluorine mold flux was solidified by an improved water-cooled copper probe with different temperatures of molten flux and different probe immersion times. The heat flux through solid films and the film structures were calculated and inspected, respectively. The results indicate: large internal cracks (formed in the glassy layer of films during solidification) were observed, the formation and evolution of those cracks contributed to the the unstable heat flux density. The roughness of the surface in contacted with the water-cooled copper probe formed as films were still glassy and the roughness have no causal relationship with crystallization or devitrification. Combeite with columnar and faceted dendritic shapes is the main crystal in the film.