The solubility mechanism of silica in a fluoride-chloride melt has been determined in situ using Raman spectroscopy. The spectroscopy data revealed that the silica solubility process involved Si-O bond breakage and Si-F bond formation. The process results in the formation of silicate complexes, fluorine-bearing silicate complexes, and silicon tetrafluoride in the melt. Mass spectrometry of the vapor phase over the KF-KCl-K2SiF6 and KF-KCl-K2SiF6-SiO2 melts and differential scanning calorimetry coupled with thermal gravimetric analysis of these melts were performed to verify the silica solubility mechanism.