The energy demand cannot be fully accomplished as the rate of increasing worldwide population is larger than the production of energy. The increasing population also leads to the development of more electrical components, which need a lot of energy to store, so energy storing devices are the need of the hour. Batteries and supercapacitors are the main class of such energy storage devices. Graphene is a 2D nanomaterial suitable for energy storage devices as electrode material due to its remarkable properties like high theoretical specific surface area and high electrical conductivity. Still, scientific works are underway to optimize the synthesis and applicability of graphene and its derivative materials in energy storage systems. This chapter discusses graphene and its derivatives for supercapacitor applications. Further, the electrochemistry behind storing energy in storage devices is discussed. This in-depth examination of graphene-based materials for energy storage may help researchers better comprehend the advantages and the most promising outcomes of such materials.