Two‐dimensional molybdenum disulfide (MoS2) nanosheets attract great interest for applications in lithium–sulfur (Li−S) batteries, due to their unique physical and chemical properties, which originate from diverse chemical compositions and unique electronic structures. In recent years, many efforts have been devoted to employing MoS2 as a polysulfide immobilizer and catalyst, functional separator, and Li‐metal protection for Li−S batteries through structural design and electronic modulation. A fundamental understanding of the interplay between structural features, electronic properties, and advanced electrochemical performance is crucial for providing valuable insights for the development of Li−S batteries. In this regard, recent advances in Li−S batteries with 2D MoS2 materials are summarized from the perspective of structural design and electronic modulation. Finally, future prospects and remaining challenges of MoS2 for Li−S batteries are highlighted.