Recent progress in the study of graphene has triggered a gold rush for exploiting its possible applications in various areas. Graphene-containing carbonaceous materials have long been selected as electrodes in rechargeable lithium batteries. However, the understanding of the relationship between material structure and electrode performance is still poor due to the complexity of the carbon structures, which hinders the development of high performance batteries. Now it is time to focus on the structure–property relationship of carbonaceous electrodes again, but from the viewpoint of graphene.