Abstract: Advanced room-temperature (RT) sodium-sulfur (Na-S) and potassium-sulfur (K-S) batteries have received widespread attention due to the abundance and low cost of corresponding raw materials and high energy density. However, their development is still restricted by serious shuttle effects, large volume expansion, and poor conductivity. To overcome these obstacles, an effective approach is to construct carbon-based materials with abundant sulfur loading space, sulfiphilic sites, high sulfur immobilization capacity, and high conductivity. Among them, hollow carbon spheres (HCSs) with adjustable structure and controllable composition shows promising prospects in advanced RT Na-/K-S batteries when used as the sulfur host. In this review, we present the recent progress in optimizing the electrochemical performance of Na-/K-S batteries by compositing HCSs strategies. First, the advantages of HCSs, their synthesis methods, and strategies for preparing HCSs/sulfur composite materials are reviewed. Second, the applications of HCSs in Na-/K-S batteries, along with mechanisms underlying the respective performance improvement, are discussed. Finally, the dilemma and perspective for the further development of HCSs for metal−S batteries are discussed. This review discusses the application of HCSs in Na-/K-S batteries and their performance enhancement mechanisms and supplies some suggestions for the future improvement of outstanding advanced metal−S batteries.