during cycling. These problems mainly result from arbitrary diffusion and thus uncontrollable deposition of intermediate lithium polysulfides (LiPSs) on the electrode surface during the solid-liquid-solid phase transfer process. [3][4][5] For enhanced anchoring strength for polar LiPSs, recently, various polar materials which have inherent adsorption ability for LiPSs such as heteroatoms-doping carbon, [6,7] polymer, [8] and metal oxides/ nitrides/sulfides, [9][10][11][12][13][14][15][16][17] have been applied on sulfur electrode. Owing to favorable sulfur-host interaction, the shuttle effect is effectively suppressed and the sulfur electrochemistry is facilitated. However, these materials only suppress the thermodynamic diffusion of LiPSs derived by the concentration gradient between cathode and electrolyte. In fact, the inherently andante reaction kinetics of LiPSs is also responsible for the shuttle effect. Aimed at the issue, recently, Arava and co-workers have first proposed the electrocatalytic approach to enhance the phase transfer kinetics of LiPSs by using catalytic metals such as Au, Pt, and Ni. [18,19] Next, the concept is extended to conductive compounds such as TiN, TiC, and CoS 2 . [20][21][22] However, the interaction of these materials with LiPSs is not very strong to mitigate the thermodynamic diffusion, moreover, the cost and preparation of these materials are high-price and complex. [21,23] Therefore, to pursue low-cost material that takes full account of both thermodynamic and kinetic dissolution of LiPSs is more effective for the practical application of LSBs.Inspired by graphene-related researches, other low-cost 2D layered materials especially transition metal sulfide/selenide (TMS) have attracted much attention in energy storage in the past years. [24] Owing to the polar feature, 2D TMS is thought to have strong bonding ability for LiPSs. [25][26][27] Moreover, according to a series of reports, the layer thickness of 2D TMS is readily regulated and various 3D structures with high surface area are easily obtained. [24] This provides abundant chemical adsorption sites to decrease the thermodynamic diffusion of LiPSs. In fact, 2D TMS have already showed the catalysis effect on solar cells, photocatalysis, and hydrogen evolution process. [28,29] This is The intrinsic polysulfides shuttle, resulting from not only concentrationgradient diffusion but also slow conversion kinetics of polysulfides, bears the primary responsibility for the poor capacity and cycle stability of lithiumsulfur batteries (LSBs). Here, it is first presented that enriched edge sites derived from vertical standing and ultrathin 2D layered metal selenides (2DLMS) can simultaneously achieve the thermodynamic and kinetic regulation for polysulfides diffusion, which is systematically elucidated through theoretical calculation, electrochemical characterization, and spectroscopic/microscopic analysis. When employed to fabricate compact coating layer of separator, an ultrahigh capacity of 1338.7 mA h g â1 is delivered after 100 cy...