Graphene nanosheets (GNSs) are prepared by oxidation and rapid expansion of graphite using microwave radiation. The prepared GNSs are characterized using various characterization tools. Morphological characterization using field emission scanning electron microscopy (FE-SEM) and transmission electron microscopic (TEM) studies revealed that the GNSs prepared through microwave radiation are crumbled with scrolled and entangled nature. Raman spectroscopy and X-ray diffraction (XRD) studies confirmed the graphitic crystalline structure of the synthesized GNSs. The surface composition and functional groups introduced on the surface of GNSs due to microwave radiation are corroborated using X-ray photoelectron spectroscopy (XPS) and Fourier transform Infrared Spectroscopy (FT-IR). Electrochemical characterization studies of GNSs based anode materials showed an enhanced lithium storage capacity and fine cycle performance. The initial discharge capacity of GNS electrode is 580mAhg−1 that decreases to 420mAhg−1 at 50th cycle. Electrochemical impedance spectral analysis reveals that the exchange current density of GNSs increases with the charge–discharge cycle numbers exhibiting the peculiar electrochemical performance.