Biomass waste-derived carbon materials are considered as high promising electrode materials in rechargable batteries since their wide sources, low costs and abundant reserves on earth. However, the structural design of these materials is still highly needed to further develop their applications in energy storage fields. In this work, peanut skin is choosen as the precursor to construct graphene-like nanosheets on the surface of porous carbon framework via a sulfuric acid-assisted hydrothermal process with following activation technique. Electrochemical results reveal this unique structure could provide high rate capacity (243 mAh·g−1 at 5 A g−1) and stable cycling performance (681 mAh·g−1 at 0.1 A g−1 after 100 cycles) in Li-ion battery and promising Na-ion storage cycling performance (233 mAh·g−1 at 0.5 A·g−1 after 450 cycles) as anodes materials. Further contrastive research indicates these promoted performance are mainly attributed to the graphene-like nanosheets in this composite structures. These sheets remarkbly enhance both of the intercalation and surface adsorption of Li-ion with high charge transfer ability, finally facilitating both of the pseudocapacitance and diffusion controlled process during the charge/discharge test. This work provides new choices for the design of nanostructures in other low cost carbonaceous materials with promoted applications in energy storage fields.