In this study, we examined the electrochemical behavior of titanium and Ti4+ compounds in THF solutions. Tetra butyl ammonium chloride (TBACl) was used as supporting electrolyte in order to increase the ionic conductivity of the solutions. Electrodeposition of pure titanium could not be obtained. A variety of analytical techniques have been used in conjunction with electrochemical methods in order to analyze the reduction process of Ti4+. These included Raman and UV-vis spectroscopy, ICP and CHNS elemental analyses. Ti4+ is being reduced to Ti3+ in TiCl4/THF/TBACl solutions. In addition we show that metallic titanium can be electrochemically dissolved from an organo-metallic electrolyte solution comprising EtAlCl2 and LiCl in THF. The product is Ti4+. While LiCl is insoluble in THF it reacts with EtAlCl2 to form ionic species. Hence, these solutions possessed reasonable ionic conductivity. We could not obtain electroactive Ti4+ with TiBr4 or TiI4 as starting materials, in similar solutions. (c) 2006 Elsevier Ltd. All rights reserved.