Nano-assisted inclusion separation of alkali metals from basic solutions was reported by inclusion-facilitated emulsion liquid membrane process. The novelty of this study is application of nano-baskets of calixcrown in the selective and efficient separation of alkali metals as both the carrier and the surfactant. For this aim, four derivatives of diacid calix[ 4]-1,3-crowns-4,5 were synthesized, and their inclusion-extraction parameters were optimized including the calixcrown scaffold (4.4%, by mass) as the carrier/demulsifier, the commercial kerosene as diluent in membrane, sulphonic acid (0.2 mol.L-1) and ammonium carbonate (0.4 mol.L-1) as the strip and the feed phases, the phase and the treat ratios of 0.8 and 0.3, mixing speed (300 r.min(-1)), and initial solute concentration (100 mg.L-1). The selectivity of membrane over more than ten interfering cations was examined and the results reveled that under the optimized operating condition, the degree of inclusion-extraction of alkali metals was as high as 98%-99%.