In order to develop an efficient and environmentally friendly process for recycling both titanium scrap and FeCl_x (x = 2, 3) waste, the chlorination-volatilization of titanium metal scraps utilizing a MgCl₂-SmCl₃ reaction-mediating molten salt was examined. After the thermodynamic analyses on the chlorination behavior of representative elements such as the alloying elements and oxygen, fundamental experiments were carried out at 1100 K by reacting off-grade Ti sponge, Ti-6Al-4V alloy rod, and Ti rod with MgCl₂-SmCl₃ molten salt. The results indicated that TiCl₄ could be effectively produced and volatilized from off-grade sponge and Ti-6Al-4V alloy. It was also confirmed that Fe and Ni in the Ti scrap remain in the molten salt as metal, whereas the Al and V in Ti alloy are chlorinated by SmCl₃ and their chlorides volatilized. Oxygen introduced into the reaction system was found to form TiOCl in the molten salt, and therefore does not consume the SmCl₃ mediator in the molten salt. These findings confirm that chlorination using a reaction-mediating molten salt is an effective means of recycling both titanium scrap and FeCl_x waste.