Four diketonate-based functional ionic liquids (ILs) with trialkylmethylammonium ([A336](+)) cation were synthesized, and the synergistic extraction systems containing IL and thetrialkylphosphineoxide (TRPO) were developed to separate Li+ from the solution generated during the Li2CO3 production by the reaction of LiCl and Na2CO3. Compared to their precursors 1,3-diketones, over the wide pH range of 1.26-10.17, ILs showed higher Li+ extractability from the solution with a high Na/Li mass ratio. Among the four ILs, the IL with 2-thenoyl-trifluoroacetonate (TTA(-)) anion showed the best Li+ separation ability. Under the optimized conditions, [A336]TTA was up to 83.26%, which was much higher than that of its precursor (71.50%). The results of slope analysis and characterizations indicated that the extracted Li+ species using the extraction systems with or without TRPO were Li2CO3 center dot 2[A336]TTA center dot TRPO and Li2CO3 center dot 4[A336]TTA, respectively. Finally, a three-stage extraction process was validated, and the recovery efficiency of Li+ from the solution provided by Qinghai CITIC Guoan Science and Technology Development Co., Ltd. (CITIC) was up to 97.16%, indicating that the extraction system of [A336]TTA + TRPO was efficient for separating lithium from the alkaline aqueous solution.