For lithium–sulfur (Li–S) batteries, the problems of polysulfides shuttle effect, slow dynamics of sulfur species and growth of lithium dendrite during charge/discharge processes have greatly impeded its practical development. Of core importance to advance the performances of Li–S batteries lies in the selection and design of novel materials with strong polysulfides adsorption ability and enhanced redox electrocatalytic behavior. Graphene, affording high electrical conductivity, superior carrier mobility, and large surface area, has presented great potentials in improving the performances of Li–S cells. However, the properties of intrinsic graphene are far enough to achieve the multiple management toward electrochemical catalysis of energy storage systems. In addition, a general and objective understanding of its role in Li–S systems is still lacking. Along this line, we summarize the design routes from three aspects, including defect engineering, dimension adjustment, and heterostructure modulation, to perfect the graphene properties. Thus-synthesized graphene materials are explored as multifunctional electrocatalysts targeting high-efficiency and long-lifespan Li–S batteries, based on which the regulating role of graphene is comprehensively analyzed. This project provides a perspective on the effective engineering management of graphene materials to boost Li–S chemistry, meanwhile promote the practical application process for graphene materials.