An effective solvent extraction-based method has been developed to recover individual platinum group metals (PGMs) (i.e. Pd, Pt and Rh) with high purity from acidic chloride media using phosphonium-based ionic liquid Cyphos IL 101 ([P₆₆₆₁₄]⁺Cl⁻) diluted in xylene used as a model of industrial diluents such as SOLVESSO 150. The system showed the selective co-extraction of Pd(II) and Pt(IV) from a feed solution containing 100 mg L⁻¹ Pt(IV), 55 mg L⁻¹ Pd(II), and 25 mg L⁻¹ Rh(III) in HCl via an anion exchange mechanism, leaving Rh(III) in the raffinate. A McCabe–Thiele diagram demonstrated the quantitative extraction of Pd(II) and Pt(IV) with 0.6 g L⁻¹ [P₆₆₆₁₄]⁺Cl⁻ with two counter-current stages at an organic/aqueous (O/A) phase volume ratio of 3/2 at 298 K. The stoichiometry of complexes formed in the organic phases was determined using Job's method and further characterized by ¹H, ¹³C, ³¹P NMR and UV-vis spectroscopy. More importantly, a two-step stripping strategy was successfully adapted to treat the loaded organic phases with low aggressive media NaSCN and thiourea/HCl for the selective recovery of Pt(IV) and Pd(II), respectively, with high purity >99.9% (w). Three counter-current stages are required for the quantitative stripping of Pt(IV) with 0.1 mol L⁻¹ NaSCN at an O/A ratio of 3, whereas the total stripping of Pd(II) with 0.01 mol L⁻¹ acidic thiourea requires only one stage at an O/A ratio of 5. A series of extraction-stripping processes of up to 5 cycles indicated a possible recirculation of regenerated solvent without loss of performance. Simulated experiments in continuous modes suggest that phosphonium-based ionic liquid such as Cyphos IL 101 can be advantageously used as extractant to recover individually Pd, Pt and Rh from acidic chloride feed solutions as those encountered in the PGM's recycling industry.