This work presents an electrochemical study of Ti3+ and Al3+ in the NaCl-KCl-AlCl3-Ti2O3 at 1123K. Transient electrochemical techniques show that Ti3+ ions are reduced to Ti metal by a two-step mechanism involving the exchanges of one and two electrons. The electrochemical co-reduction of Ti3+ and Al3+ in the NaCl-KCl-AlCl3-Ti2O3 melts at 1123 K was performed. Cyclic voltammetry and square wave voltammetry were applied using a molybdenum electrode to investigate the reduction behavior of Ti3+ and Al3+ and to identify the Ti-Al alloys. A series of redox signals corresponding to different Ti-Al alloys were observed. Potentiostatic electrolysis was conducted using a molybdenum electrode to prepare the Ti-Al alloys. The obtained deposits were characterized by SEM-EDS and XRD. Compounds Layers of TiAl3 and TiAl2 were generated via potentiostatic electrolysis. (C) 2015 Elsevier Ltd. All rights reserved.