The formation of Si(II) by the comproportionation reaction between electrodeposited silicon and Si(IV) ions [Si(IV) + Si 0 ⇄ 2Si(II)] in fluoride melts has been discussed in many previous reports on the electrochemical processing of silicon. In this study, the coordination structure of Si(II) ions in LiF−KF, LiF− NaF, NaF−KF, and LiF−NaF−KF melts was investigated by hightemperature Raman spectroscopy and quantum chemical calculation based on density functional theory. The formation of Si(II) ions was induced by mixing metallic silicon powder as the source of Si 0 , with the melts containing hexafluoro silicate or silicon dioxide as the source of Si(IV) ions. The simulated vibrational modes of the Si(II) species and the experimental Raman bands showed good agreement. It was found that both Si(II) and Si(IV) species were detected in either fluoride melt, demonstrating that the proposed comproportionation reaction between Si 0 and Si(IV) occurred. In addition, the interaction between Si(II) and F − , O 2− , Li + , Na + , and K + ions significantly changed depending on the composition of fluoride melts. The coordination structure of the Si(II) ions reported in this study will provide clues for controlling the electrodeposition process of silicon in fluoride melts.