Abstract Lithium–sulfur (Li–S) batteries have been considered as promising battery systems due to their huge advantages on theoretical energy density and rich resources. However, the shuttle effect and sluggish transformation of soluble lithium polysulfides (LiPSs) hinder the practical application of Li–S batteries. Tremendous sulfur host materials with unique catalytic activity have been exploited to inhibit the shuttle effect and accelerate LiPSs redox reactions, in which theoretical simulations have been widely adopted. This review aims to summarize the fundamentals and applications of theoretical models in sulfur cathodes. Concretely, the integration of theoretical models provides insights into the adsorption and conversion mechanisms of LiPSs and is further utilized in the smart design of catalysts for the exploitation of practical Li–S batteries. Finally, a perspective on the future combination of calculation technology and theoretical models is provided.
