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β-Diketones are often used to separate brine with a high sodium-to‑lithium ratio but cannot be widely used because of their high toxicity and water solubility. In this work, a functionalized ionic liquid was synthesized from 4,4,4-trifluoro-1-phenyl-1,3-butanedione and 1-hexyl-3-methylimidazolium chloride, which was verified by FT-IR and 1H NMR spectroscopy. An organic phase system was formed with this ionic liquid as the extractant and 2-octanone as the diluent, which had the advantage of achieving good extraction and separation performances without co-extractant. In addition, the brine used in this work is the real Chaka salt lake brine in Tibet, which provides a reference value for industrial application of separation of metal ions. The experimental conditions were optimized and the single-stage extraction efficiency of Li+ reached up to 94 %. Using LiCl solution and HCl as the washing and stripping reagents, the washing efficiency of Na+ and stripping efficiency of Li+ were above 98 % and 99 %, respectively. The raffinate was used to regenerate the organic phase, which reduced the use of alkaline reagents. Over 10 cycles of the extraction process, the extraction efficiency of Li+ maintained at approximately 86 %. The extraction mechanism was identified as ionic association using slope analysis and ultraviolet and infrared measurements. • A novel extraction system was developed for selective extraction of lithium from Tibetan brine. • The single-stage extraction efficiency of Li+ with the extraction system reached up to 94 %. • The impurity ions could be washed out by using LiCl solutions. • The raffinate could be used to regenerate the organic phase. • The extraction system showed good reusability over 10 cycles of the extraction process. [ABSTRACT FROM AUTHOR]