NaClKClTiCl x was prepared via using titanium sponge to reduce titanium tetrachloride in a NaClKCl melt under a negative pressure at 1023 K. The relationship between titanium valence states and [F]/[Ti] molar ratios was investigated with successive adding potassium fluoride in the pre-prepared NaClKClTiCl x . It was found that the average valence of titanium ions tended to be stable around 3.0 when [F]/[Ti] molar ratio was greater than 1.80. The equilibrium redox potentials, E Ti 3þ =Ti 2þ , E Ti 4þ =Ti 3þ , E Ti 3þ =Ti and E Ti 2þ =Ti , were also calculated through the obtained concentration of equilibrium titanium ions with different molar ratios of [F]/ [Ti]. Meanwhile, the influence of the fluoride anion on over-potential and characteristics of titanium electrodeposition were investigated through changing the molar ratio of [F]/ [Ti]. The results showed that, with the increasing of [F]/[Ti] molar ratios, the grain size of electrodeposition products became smaller, while the over-potential was higher.