opment of new energy storage technologies. [1] Sulfur is an abundant, inexpensive, and environment-friendly element which can deliver a high specific capacity of 1675 mAh g -1 through its conversion mechanism. [2] Lithium-sulfur (Li-S) batteries are therefore regarded as the most promising next-generation lithium battery due to their high energy density of 2600 Wh kg -1 . [3] Although Li-S batteries have been widely studied in the past two decades, they still face many challenges in safety, performance, and lifespan for industrial commercialization. The most serious challenge is the dissolution and diffusion of lithium polysulfides (LiPSs) in conventional ether-based electrolytes. [4] The dissolved LiPSs diffuse to and chemically corrode lithium anodes, causing severe loss of active materials and rapid capacity decay. [5] Many scientists have demonstrated that chemisorption and electrocatalysis with the use of highly porous carbon, metal oxides/carbides/ sulfides/nitrides, or other polar materials are effective strategies to inhibit the shuttle effect. [5a,6] However, it should be noted that these strategies can only relieve but cannot eliminate the dissolution of LiPSs in ether solvents from a thermodynamic point of view. [7] Enabling a solid-phase conversion mechanism of sulfur could help avoid the production of soluble intermediate LiPSs. Several studies have demonstrated that carbonate-based Li-S batteries using sulfurized polyacrylonitrile (S@pPAN) or microporouscarbon/small-sulfur cathodes show enhanced safety and stable cycling performance by eliminating the production of LiPSs. [8] The carbonate-based electrolytes possess high ionic conductivity, wide electrochemical window, high volatilization temperature, are commercially mature, and have wide application, showing great promise for replacing ether-based electrolytes in Li-S batteries. [9] Unfortunately, most sulfur cathodes are chemically incompatible with carbonate-based solvents due to the irreversible nucleophilic attack at carbonyl carbon atoms by LiPSs. However, some sulfur cathodes can be paired with carbonate electrolytes if the cathodes have small sulfur molecules confined within a microporous structure or strongly chemically bonded to a polymeric host, which will limit the sulfur mass content (<50 wt%) and areal loading in cathodes, thereby compromising energy density. [10] A molecular layer deposition Lithium-sulfur (Li-S) batteries have attracted significant attention because of their high theoretical energy density and low cost. However, their poor cyclability caused by the shuttle effect in ether-based electrolytes remains a great challenge for their practical application. Herein, a novel electrolyte is proposed by combining widely used carbonate solvents diethyl carbonate/fluoroethylene carbonate and inert diluent 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether for Li-S batteries based on typical mesoporous carbon/sulfur (KB/S) materials. Differing from the conventional dissolution-precipitation mechanism, the sulfur cathodes ...