The structural effects of graphene on the electrochemical properties of graphene-based ultracapacitors are investigated for the first time, where the competitive impacts resulting from the edge content, specific surface area, edge/basal defects, oxygen-containing groups and metal oxides/surfactant impurities are taken into consideration, demonstrating that not one element, but all are responsible for the final behavior of graphene-based ultracapacitors. This work will be of wide importance to research producing graphene-based energy storage/generation devices.