The solvent extraction of Li + by Cyanex 923 was investigated upon the addition of different imidazolium-based ionic liquids (ILs). The results showed 1-hydroxylethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([HOEmim][NTf 2 ]) can improve the extraction of Li + most effectively. The fundamental mechanism is that [HOEmim] [NTf 2 ] can remarkably enhance the coordination ability of Cyanex 923 to Li + to form more stable and hydrophobic ion-pair species [Li(Cyanex 923) n ][NTf 2 ] (n max = 3) resulting from the electrostatic interaction and typical hydrogen bonding of IL, and thus facilitating the transfer of Li + into organic phase. This work has revealed the transfer mechanism of Li + in a solvent extraction system comprising of IL and neural ligand. The knowledge of the coordination environment of Li + in the presence of IL also gives us a new insight into the separation of 6 Li/ 7 Li. The disadvantage of this process is the loss of IL. However, this study provides guidance for the design of better IL-based systems for the separation of metal ions. K E Y W O R D S extraction, ionic liquids, lithium, trialkylphosphine oxide 1 | INTRODUCTION Lithium (Li) is a strategic metal. It has a wide variety of applications in the area of nuclear energy, 1 aeronautics and astronautics, lithium batteries, 2 glasses, and ceramics. With the growing market in electronics and new