A preheated high-temperature environment is believed to be critical for a chemical-exfoliation-based production of graphenes starting from graphite oxide, a belief that is based on not only experimental but also theoretical viewpoints. A novel exfoliation approach is reported in this study, and the exfoliation process is realized at a very low temperature, which is far below the proposed critical exfoliation temperature, by introducing a high vacuum to the exfoliation process. Owing to unique surface chemistry, low-temperature exfoliated graphenes demonstrate an excellent energy storage performance, and the electrochemical capacitance is much higher than that of the high-temperature exfoliated ones. The low-temperature exfoliation approach presents us with a possibility for a mass production of graphenes at low cost and great potentials in energy storage applications of graphene-based materials.