In recent years, biomass-derived carbon in the energy storage system has attracted tremendous attention due to low cost, scalable, meso/microporous nature. Here we describe the synthesis of peanut shell activated carbon (PSAC) by scalable and low power microwave method using KOH as an activation agent. The structural, surface area, porosity, and morphological properties of PSAC are characterized by different techniques such as XRD, Raman, XPS, N-2 adsorption/desorption, FESEM and HRTEM analysis. FESEM and HRTEM confirm the highly distributed interconnected hierarchically porous structure with uniform nanopores over the surface and the achieved high surface area of PSAC is 525.685 m(2) g(-1). Furthermore, the PSAC is explored as an anode electrode material for Li-ion batteries (LIBs). The obtained reversible capacity is 680 mAh g(-1) at 0.05 C rate after 100 cycles. The achieved rate capability, high reversible capacity and stability of the PSAC electrode mainly depend on its excellent conductivity, high surface area, rich porosity, more edges defects sites and hierarchically porous structured morphology.