The impact of varying F content from 4 wt% to 10 wt% on the structure and properties of non-reactive mold slag for high-Mn high-Al steel was investigated in this study. Employing a combination of techniques including a rotary viscometer, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and Raman spectroscopy, the viscosity and structure of mold slag were analyzed. The findings revealed that increasing F content led to a gradual reduction in viscosity, activation energy for viscous flow, and the internal friction within the mold fluxes, consequently enhancing its fluidity. The Al–O–Al structure remained stable throughout the experimental range. The decrease in QAl2 content indicated a continuous depolymerization process, leading to the formation of free [Al2OF6] and [AlO6] structures as F content increased. At the same time, the replaced O2− ions were assimilated by [AlO4] tetrahedron, facilitating the formation [AlO6] octahedron. Consequently, the slag structure was simplified, resulting in a reduction in the degree of polymerization and viscosity.