Lithium-sulfur batteries (LSBs) are attractive candidates for post-lithium-ion battery technologies because of their ultrahigh theoretical energy density and low cost of active cathode materials. However, the commercialization of LSBs remains extremely challenging primarily due to poor cycling performance and safety concerns, which are inherently caused by low conductivity of S8 and Li2S, severe polysulfide shuttling, and high polarization by solid Li2S2/Li2S deposition. Catalytic materials could facilitate the large-scale practical application of LSBs by overcoming all these challenges. In this review, we investigate the sulfur species evolution in LSBs and explore the roles of catalytic materials in charge/discharge processes, highlighting the catalysis of solid S8 to liquid polysulfides and solid Li2S2 to Li2S. Furthermore, we offer systematic strategies from atomic to macro levels, including defect engineering, morphology engineering and catalyst compositing, to enhance catalysis efficiency in terms of sulfur supercooling, fast charge transfer, thiosulfate generation, disulfide bond cleavage, tuneable Li2S growth and Li2S decomposition enhancement. The design and availability of the proposed catalytic materials will further advance LSB technology from coin cells and pouch cells to the subsequent commercialization scale.