Electronic absorption spectra of vanadium ions were recorded between 450 and 750 degrees C in 3LiCl-2KCl, NaCl-KCl and NaCl-2CsCl based melts. Analysis of the spectra showed that vanadium in the oxidation states of +2 and +3 is present in the melts as complex chloro-ions. Vanadium(II) can form the complex ions in octahedral and tetrahedral coordination, the latter being favored by higher temperatures. Only six-coordinated V(III) ions were observed. Vanadium in the oxidation state of +4 can be present in chloride melts only in the form of vanadyl-based oxochloro-species. Main spectroscopic parameters of vanadium complex ions were determined. Electronic absorption spectroscopy was also applied for studying a variety of the red-ox processes in vanadium containing melts including electrochemical oxidation and reduction of various species, and reaction of vanadium containing melts with oxygen. (C) The Author(s) 2017. Published by ECS. All rights reserved.