Graphene has attracted tremendous attention in recent years in different fields of application. Graphene and its derivatives can be functionalized by employing numerous approaches to produce graphene-based materials with tuned properties. Among their applications, functionalized graphene materials have demonstrated considerable improvements of the performance of lithium–sulfur batteries as an additive in the cathode composite, as an interlayer on the separator, and as a protecting coating on the anode. Graphene is interesting for Li–S battery applications owing to its unique combination of properties, such as high electrical and thermal conductivity, exceptional mechanical strength, impermeability, and the ability to be readily chemically modified. For these reasons, graphene materials can be found in cathodes, where they provide good electronic conductivity, cathode flexibility, and impermeability toward lithium polysulfide species. Similarly, graphene-based materials are used as interlayers close to the battery separator and as a host or an artificial solid electrolyte interface on the anode side. Specifically, graphene-based materials greatly impact the Li–S battery performance in terms of a higher C-rate capability, capacity stability, and improved Coulombic efficiency. The following book chapter summarizes the work carried out in the field of graphene-based materials and its derivatives used as battery components in terms of the Li–S battery performance.