Graphene nanosheets are synthesized by a novel facile method involving freeze-drying technology and thermal reduction. The microstructure and morphologies are characterized by X-ray diffraction, Brunauer–Emmett–Teller measurements, Fourier transform infrared spectroscopy, and high resolution transmission electron microscope. The results indicate that graphene nanosheets with high specific surface area (358.3 m2 g−1) and increased interlayer distance (0.385 nm) are successfully obtained through the freeze-drying process. The electrochemical performances are evaluated by using coin-type cells versus lithium. A high initial reversible capacity of 1132.9 mAh g−1 is obtained at a current density of 100 mA g−1. More importantly, even after 300 cycles at a high current density of 1000 mA g−1, a stable specific capacity of 556.9 mAh g−1 can be achieved, suggesting the graphene nanosheets exhibit superior cycle stability. The fascinating electrochemical performance could be ascribed to the high specific surface area and the increased layer distance between the graphene nanosheets.