Smelting reduction of spent lithium-ion batteries (LIBs) produces metallic alloys containing Co, Ni, Cu, Mn, and Fe. Finding suitable reagents in terms of efficiency, economics, and friendly environment for the dissolution of these metals from the alloys is very important for the recovery process of the metals. In this work, the employment of ferric chloride solution for the dissolution of the metals from the alloys was studied. The effect of parameters like FeCl₃ concentration, temperature, time, and pulp density on the leaching efficiency of metals was investigated. Our results indicate that ferric ions in the leaching solutions act as oxidizing agents for the dissolution of the metals, while chloride anions as ligands for the formation of the complexes of the dissolved metal ions. The best conditions for the dissolution of full metals were 0.7 mol/L FeCl₃, 12.5 g/L pulp density, 22^oC, and 30 min. In comparison with HCl or H₂SO₄ leaching agents, ferric chloride shows some advantages like a decrease in the dosage of acids and oxidizing agents, fast reaction kinetics, and low energy consumption. With its advantages, ferric chloride solution is considered a potential leaching agent in the recovery process of valuable metals from spent LIBs.