X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy were used to analyze the complexes in LiCl-KCl eutectic salt containing VCl₃ and KF. The additional fluoride ions would replace chloride ions and combine with V(III) to form VF₆^3-. The electrochemical behavior of V(III) was evaluated under condition of the molar concentration ratio of F^- to Vⁿ⁺ (α) equal to 0:1, 1:1, 2:1, 5:1, 20:1 and 50:1, respectively. The results showed that a new reduction step appeared: VF₆^3-→V²⁺, and the reduction mechanism of vanadium ions became more complicated. The metallic vanadium was deposited on the tungsten electrode at -2.90 V in the LiCl-KCl melts for 6 h, and the products were characterized by SEM-EDS. It was indicated that the particle size of the product decreased with adding fluoride ions for the forming of the coordination compound VF₆^3-.