The extraction of ReO₄^- and TcO₄^- by ionic liquids (ILs) were investigated systematically. The results indicated that imidazolium and quaternary ammonium ILs could extract ReO₄^- and TcO₄^- efficiently via anion-exchange mechanism. Compared with NTf₂-based ILs, PF₆-based ILs had a higher extraction efficiency towards ReO₄^- and TcO₄^-. With respect to the ILs with an identical anion, the extraction efficiency increased with the increase of the chain length of IL’s cations. The addition of HNO₃ and IL’s anion in aqueous phase decreased the extraction efficiency, while the increase of the concentration of IL’s cation led to an opposite effect. At a lower concentration of nitric acid, ReO₄^- ions were selectively extracted by either [N_6,444][NTf₂] or [C₈mim][PF₆] from simulated liquid waste. KPF₆ and LiNTf₂ aqueous solutions can strip ReO₄^- effectively from [C₈mim][PF₆] and [N_6,444][NTf₂], respectively.