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 calixarene in the selective and efficient separation of alkali metals as both the carrier and the surfactant. For this aim, four derivatives of p-tert-calix [4]arene bearing different sulfonamide moieties were synthesized and their inclusion-extraction parameters were optimized. 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%.