The shuttle effect of soluble polysulfides is a serious problem impeding the development of lithium−sulfur batteries. Herein, continuous amino-functionalized University of Oslo 66 membranes supported on carbon nanotube films are proposed as ion-permselective interlayers that overcome these issues and show outstanding suppression of the polysulfide shuttle effect. The proposed membrane material has appropriately sized pores, and can act as ionic sieves and serve as barriers to polysulfides transport while allowing the passage of lithium ions during electrochemical cycles, thereby validly preventing the shuttling of polysulfides. Moreover, a fast catalytic conversion of polysulfides is also achieved with the as-developed interlayer. Therefore, lithium−sulfur batteries with this interlayer show a desirable initial capacity of 999.21 mAh·g^–1 at 1 C and a durable cyclic stability with a decay rate of only 0.04% per cycle over 300 cycles. Moreover, a high area capacity of 4.82 mAh·cm^–2 is also obtained even under increased sulfur loading (5.12 mg·cm^–2) and a lean-electrolyte condition (E/S = 4.8 μL·mg^–1).