In the continuous casting of steel, mold fluxes play an important role in improving surface quality of casting strands and maintaining the continuous casting process. The physiochemical property of mold fluxes is definitely correlated with the microstructure. Fluorides play an important role in modifying the high temperature properties of mold fluxes. So, studying the effect of fluoride on multicomponent silicate structure is helpful to understanding the performance of fluoride in mould fluxes. In the present paper, effects of fluorine on melt, glass and crystal structure of silicate were studied by using Raman spectroscopy and in situ high temperature technique. The results were as follows: While the content of CaF2 increased, the varieties and relative quantities of microstructural units of silicates changed, the polymerization of the silicate network decreased, and the viscosity of the melt decreased; comparing non-fluoride with high-fluorine mold fluxes, the main kind of microstructure of silicates in mold fluxes with high fluorine was mostly monomer, while in fluorine free mold fluxes it was mainly chain of microstructure. It would help to develop fluorine free mold fluxes.