In recent years, the demand for high-performance rechargeable lithium batteries has increased significantly, and many efforts have been made to boost the use of advanced electrode materials. Since graphene was first isolated by Novoselov et al., graphene/graphene-based materials have become an active area of research and are considered to be promising high-performance electrode materials. Graphene is a two-dimensional single-atom carbon-packed material that possesses fascinating properties, including a large surface area, remarkable electrical conductivity, extraordinary intrinsic electron mobility, high Young's modulus, superior mechanical strength, optical transmittance, catalytic performance, and stability. Therefore, graphene is considered an attractive material for rechargeable lithium-ion batteries (LIBs), lithium-sulfur batteries (LSBs), and lithium-oxygen batteries (LOBs). In this comprehensive review, we emphasise the recent progress in the controllable synthesis, functionalisation, and role of graphene in rechargeable lithium batteries. Finally, in this review, we aim to address the most promising results, benefits, challenges, critical issues, research directions, and perspectives to explain the developmental directions of graphene for batteries.