This perspective discusses the role of electrocatalytic materials in developing post-lithium metal||sulfur (M||S) batteries. Post-lithium M||S batteries offer high theoretical specific energy, making them promising for large-scale energy storage. However, challenges such as polysulfide shuttle effects, slow kinetics, and poor cycling stability hinder their practical application. The article provides a comprehensive analysis of key parameters, including S mass loading, S content, electrolyte/S ratio, and negative/positive electrode capacity ratio, to optimize the specific energy of these batteries. It also evaluates the progress in using homogeneous and heterogeneous electrocatalytic approaches to enhance sulfur conversion in both non-aqueous and aqueous M||S systems. The study highlights the importance of electrocatalytic materials in improving the electrochemical performance of post-lithium M||S batteries, with a focus on designing practical systems for real-world applications. The article also discusses the challenges and future directions for developing post-lithium M||S batteries, including the need for efficient electrolytes, functional separators, and stable negative electrodes. The role of electrocatalytic materials in enhancing sulfur conversion and improving battery performance is emphasized, with a focus on achieving high specific energy and long-term cycling stability. The study concludes that while post-lithium M||S batteries face significant challenges, they hold great potential for large-scale energy storage due to their high theoretical energy density and the abundance of sulfur. The development of efficient electrocatalytic materials and electrolytes is crucial for overcoming these challenges and realizing the practical application of post-lithium M||S batteries.This perspective discusses the role of electrocatalytic materials in developing post-lithium metal||sulfur (M||S) batteries. Post-lithium M||S batteries offer high theoretical specific energy, making them promising for large-scale energy storage. However, challenges such as polysulfide shuttle effects, slow kinetics, and poor cycling stability hinder their practical application. The article provides a comprehensive analysis of key parameters, including S mass loading, S content, electrolyte/S ratio, and negative/positive electrode capacity ratio, to optimize the specific energy of these batteries. It also evaluates the progress in using homogeneous and heterogeneous electrocatalytic approaches to enhance sulfur conversion in both non-aqueous and aqueous M||S systems. The study highlights the importance of electrocatalytic materials in improving the electrochemical performance of post-lithium M||S batteries, with a focus on designing practical systems for real-world applications. The article also discusses the challenges and future directions for developing post-lithium M||S batteries, including the need for efficient electrolytes, functional separators, and stable negative electrodes. The role of electrocatalytic materials in enhancing sulfur conversion and improving battery performance is emphasized, with a focus on achieving high specific energy and long-term cycling stability. The study concludes that while post-lithium M||S batteries face significant challenges, they hold great potential for large-scale energy storage due to their high theoretical energy density and the abundance of sulfur. The development of efficient electrocatalytic materials and electrolytes is crucial for overcoming these challenges and realizing the practical application of post-lithium M||S batteries.