Hydrophilic ionic liquids, 1-alkyl-3-methylimidazolium chloride ([C(n)mim]Cl, n = 12, 14, and 16) are tested to precipitate Pt(IV) from hydrochloric acid medium. Meanwhile the Pt(IV) extractions are performed with hydrophobic ionic liquids, including 1-alkyl-3-methylimidazolium hexafluorophosphate ([C(n)mim]PF6, n = 4, 6, and 8) and 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C(8)mim]NTf2). Based on Jobs method, infrared spectra, and 1H NMR analysis, the anion-exchange mechanism is confirmed during the Pt(IV) precipitation. The mixed hydrophilic-hydrophobic ionic liquids ([C(n)mim]Cl/[C(8)mim]PF6) are developed for Pt(IV) extraction, which significantly increase the Pt(IV) extractability compared to the single hydrophobic ionic liquid. Under the optimum conditions, the [C(16)mim]Cl/[C(8)mim]PF6 system shows high extractability as well as outstanding selectivity for Pt(IV) over the base metals (Mn(II), Cu(II), Co(II), Ni(II), Fe(III), and Al(III)). By reductive stripping, Pt(IV) in the organic phase can be stripped in the form of platinum powders using hydrazine hydrate; at the same time [C(16)mim]Cl is regenerated in the organic phase. The mixed [C(16)mim]Cl/[C(8)mim]PF6 ionic liquids can be reused to extract Pt(IV). Therefore, the method is highly effective, selective, and recyclable to extract Pt(IV) and recover metal platinum.