Highlights The review emphasizes the formation of trisulfur radicals in solid-state lapis lazuli analogs and the role of high donor number solvents and/or their co-solvents in stabilizing trisulfur radicals. The detection techniques are also discussed for monitoring the generation of trisulfur radicals, which are critical for understanding their behavior and optimizing the design of lithium–sulfur batteries. The strategies involving both homogeneous and heterogeneous catalysts are summarized to increase the generation of trisulfur radicals and enhance catalytic reactions in lithium–sulfur batteries for practical applications.