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The extraction behavior of V(Ⅴ) along with Cr(Ⅵ) by pure hydrophobic ionic liquid [C8mim][PF6] has been investigated.[C8mim][PF6] shows a good extraction ability for V(Ⅴ) while slight for Cr(Ⅵ).The extraction of V(Ⅴ) is strongly dependent on the acidity of the aqueous phase,and the maximum separation factor between V and Cr (βV/Cr) was calculated to be 100.58 in case of pH 3.5,which is higher than the traditional primary amine liquid-liquid extraction system.Moreover,the stripping of V(Ⅴ) from IL phase has also been investigated.The V(Ⅴ) in IL phase can be quantitatively stripped by KPF6 solution under the basic condition ([OH-] = 1 mol/l).Finally,the pure [C8mim][PF6] as extracting phase has been used to separate vanadium(Ⅴ) from the real industrial effluent containing chromium(Ⅵ),and it is confirmed that the selective extraction of V(Ⅴ) from the diluted industrial effluent is possible.