Lithium–sulfur batteries (LSBs) with a high theoretical capacity of 1675 mAh g−1 hold promise in the realm of high‐energy‐density Li–metal batteries. To cope with the shuttle effect and sluggish transformation of soluble lithium polysulfides (LiPSs), varieties of traditional metal‐based materials (such as metal, metal oxides, metal sulfides, metal nitrides, and metal carbides) with unique catalytic activity for accelerating LiPSs redox have been exploited to fundamentally inhibit the shuttle effect and improve the performance of LSBs. Concurrently, some budding catalytic materials also possess enormous potential for facilitating LiPSs redox reaction in LSBs, including metal borides, metal phosphides, metal selenides, single atoms, and defect‐engineered materials. Here, recent advances in these emerging catalytic candidates as well as the evaluation methods and parameters for catalytic materials are comprehensively summarized for the first time. New insights are also given to aid in the design of high‐performance LSBs and satisfy the high expectation in the future, including the exposure of the active sites and adsorption‐catalysis synergy strategies. Finally, the current challenges and prospects for designing highly efficient catalytic materials are highlighted, aiming at providing guidance for configuring catalytic materials to make sure high‐energy and long‐life LSBs.