Study of corrosion phenomena associated with the use of molten salts as coolants raised interest in the behaviour of various metal ions in such melts. Gruen & McBeth1, in the early sixties, studied various transition metal ions in LiCl/KCl eutectic. The purpose of the present letter is an attempt to correlate ESR data with data derived from optical spectroscopy, in particular with respect to the equilibrium between hexa- and tetra-coördinate species of Ti(III) with chlorine ions.