In this work, cotton fabric was used as a template to create macro sheets of graphene. The cotton fabric was dipped into a graphene/pyrene-derivative suspension. The graphene-coated cotton textile was then annealed at a high temperature in a quartz tube furnace under argon flow. During the annealing process, the gaps between separated graphene sheets were “soldered” by the “glue” molecules (aromatic molecular surfactants) to form graphene-coated pyrolytic carbon. The result was a graphene “skin” created on the pyrolytic carbon scaffold that is flexible graphene coat and can contribute relatively high capacity to a lithium battery sandwich. This occurs because of porous structure of graphene sheets and the high surface area of the pyrolyzed carbon with a shell-core structure. This novel, facile, and low-cost method can be expanded to applications on other carbon-rich materials such as peanut shells, wood waste and other cellulosic waste materials.