Nanostructured carbon materials, including carbon nanotubes, graphene and nanoporous carbon, show promise for expanding renewable energy. In particular, the configuration and electronic properties of graphene edges in relation with their electrochemical activity have become a major issue in carbon-based energy storage devices. Here, we review recent results concerning the important roles of graphene edges as the gateway for lithium ion intercalation in the anode of lithium-ion batteries, as promoters of high capacitance in carbon-based supercapacitors, and as anchoring sites for Pt nanoparticles in fuel cells. We envisage that the controlled synthesis of a specific, clean, and stable edge configuration could be achieved to maximize the electrochemical performance of nanostructured carbon-based energy storage devices.