The solvent extraction for the separation of platinum group metals from the leach liquor of spent automotive catalysts has been studied. Tri-n-butyl phosphate (TBP), tri-n-octylamine (TOA) and di-n-hexyl sulfide (DHS) were used as extractants and kerosene as a diluent. The extraction behavior of platinum, palladium and rhodium has been investigated as functions of different kinds of extractants and their concentrations. In addition, the extraction behavior of the major metal impurities such as cerium, lead, iron, magnesium and aluminum has been investigated. Platinum and palladium were extracted with TBP. And platinum, palladium and rhodium were extracted with TOA. Platinum was co-extracted with palladium into the organic phase by solvent extraction using SFI-6 of DHS extractant, but only palladium was selectively extracted with SFI-6R. The selective extraction of palladium with SFI-6R was found better than that with SFI-6, but the kinetics of extraction with SFI-6R was found poor in comparison to SFI-6. The metal impurities extracted simultaneously during the extraction of platinum group metals should be removed in scrubbing and stripping processes. A suitable process has been proposed for the separation of platinum group metals from the leach liquor of spent automotive catalysts. Initially palladium was extracted with SFI-6R, followed by the separation of platinum with TBP or TOA leaving rhodium in the raffinate.