Platinum group metals (PGMs) play an important role in the automotive industry as key components of exhaust catalysts. Recycling of PGMs from secondary resources, such as waste products, is encouraged to ensure their sustainability. A highly efficient and environmentally benign technique for the separation of PGMs is currently required. In the present study, the recovery of PGMs from a spent automotive catalyst was investigated using the trioctyldodecyl phosphonium chloride (P8,8,8,12Cl) ionic liquid (IL) as the PGM extraction solvent. First, leaching P8,8,8,12Cl from the catalyst was investigated. Pt and Pd are selectively extracted into undiluted from the mol L-1 HCI leachate containing various metals together with Pt, Pd, and Rh. Subsequently, Rh is extracted into fresh P8,8,8,12Cl from the raffinate adjusted to an appropriate HCl concentration. Mutual separation of Pt and Pd is possible by stripping processes. Some common metals coextracted with PGMs, such as Fe, Cu, and Zn, are removed by each stripping process. Recovery of high purity Pt, Pd, and Rh is achieved by the proposed recycling process. The results demonstrate that separation using phosphonium-based ILs is useful for recycling PGMs.