Catalytic conversion of polysulfides is regarded as a crucial approach to enhancing kinetics and suppressing the shuttle effect in lithium–sulfur (Li–S) batteries. However, the activity prediction of Li–S catalysts remains elusive owing to the lack of mechanistic understanding of activity descriptors. Here, we report a volcano-shaped relationship between polysulfide adsorption ability and catalytic activity. In conjunction with theoretical analysis, we distinguish catalytic and anchoring effects to delineate the role of adsorption and emphasize the passivation of catalysts. These findings enable us to develop a composite catalyst, Co_0.125Zn_0.875S, which shows higher performance than simple binary compounds. Such a fundamental understanding of the intrinsic link between polysulfide adsorption and catalytic activity offers a rational viewpoint for designing Li–S catalysts and tuning their activities.

多硫化物的催化转化被认为是提高锂硫（Li-S）电池动力学和抑制穿梭效应的关键方法。然而，由于缺乏对活性描述符的机理理解，Li-S 催化剂的活性预测仍然难以捉摸。在这里，我们报告了多硫化物吸附能力和催化活性之间的火山形关系。结合理论分析，我们区分催化和锚定效应以描述吸附的作用并强调催化剂的钝化。这些发现使我们能够开发复合催化剂 Co _0.125 Zn _0.875S，比简单的二元化合物表现出更高的性能。这种对多硫化物吸附和催化活性之间内在联系的基本理解为设计 Li-S 催化剂和调整其活性提供了合理的观点。