Distance‐Matched Spatially Separated Bimetallic Centers in a Covalent Organic Framework Accelerate Polysulfide Conversion in Lithium−Sulfur Batteries

Developing catalysts with tailored metal centers targeting long‐chain lithium polysulfides (LiPSs, ∼5.4–5.8 Å) is critical for suppressing shuttle effect and accelerating sluggish redox kinetics in lithium−sulfur batteries (LSBs). However, the spatially compact configurations of conventional metal sites often impose constrained binding geometries, thereby weakening metal−sulfur interactions and limiting catalytic activation. Here, we report a covalent organic framework (COF) catalyst featuring spatially separated bimetallic centers (SSBC‐COF) with an intersite distance of 5.8 Å, constructed by coordinating metal ions at two adjacent yet distinct chelating sites within COF. The dual‐site coordination design increases the density of accessible Cu sites, while the distance‐matched bimetallic configuration enables simultaneous interactions with multiple sulfur atoms. As a result, SSBC‐COF delivers markedly enhanced polysulfide confinement and conversion. The LSBs employing SSBC‐COF achieve a 270% higher discharge capacity and improved cycling stability with a 65% lower capacity‐decay rate than that with PP separator. Moreover, an ultrahigh areal capacity of 14.5 mAh cm −2 is obtained at a high sulfur loading of 12.7 mg cm −2 under lean‐electrolyte conditions. This work establishes spatially separated bimetallic centers as an effective design principle for advanced porous catalysts toward high‐performance LSBs.