Graphene-based materials have emerged as exceptional candidates for the development of novel, high performance actuators. Developing such an actuation material requires an in depth knowledge of the physics of operation and, therefrom, how to best optimize its performance. We investigate the electromechanical actuation of pristine monolayer graphene to elucidate the origin of this material’s exceptional electromechanical actuation performance. It is shown that the electrostatic double-layer (EDL) effect is dominant compared to the quantum-mechanical (QM) effect upon charging and electrolyte immersion. Seeking to optimize the QM actuation performance, we preliminarily investigate graphene oxide (GO) as a potential graphene-based actuation material, and find that it exhibits both unique and high performance responses. Having demonstrated huge stresses (~100 GPa) and high strains (~0.4%), graphene-based materials are uniquely positioned to address future industrial actuation challenges.