Sulfur cathodes for lithium–sulfur batteries have been designed to be combined with conductive carbon because the insulating nature of sulfur causes low active material utilization and poor rate capability. This paper is the first to report that carbon can induce a phase transition in a sulfur cathode. The stable form of a sulfur crystal at ambient temperature is orthorhombic sulfur. We found that monoclinic sulfur becomes more stable than orthorhombic sulfur if carbon atoms penetrate into the sulfur at elevated temperatures and the carbon density exceeds a threshold of C0.3S8. The high stability of the carbon-containing monoclinic sulfur persists during lithiation and is attributed to locally formed linear SC3S chains with marked stability. This study provides a novel perspective on the role of carbon in the sulfur cathode and suggests control of the crystal phase of electrodes by composite elements as a new way of designing efficient electrode materials.