In this work, silicon (Si) containing carbon coated core-shell nanostructures were synthesized by electrical explosion of Si wires in ethanol solution followed by high energy mechanical milling (HEMM) process. Material characterization was carried-out using transmission electron microscopy (TEM), field-emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD) analysis. HEMM led to very fine and amorphous Si particles in the presence of carbon and inactive Silicon-Carbide (SiC) matrix. These Si based nanocomposites, obtained through electrical explosion followed by HEMM (milled sample), exhibited enhanced electrochemical performance than unmilled nanocomposites, when evaluated as anode material for lithium-ion batteries (LIBs). On completion of (the) 1st cycle, milled and unmilled sample(s) showed specific discharge capacities around 825 mAh/g and 717 mAh/g, respectively. Interestingly, the coulombic efficiencies of milled and unmilled samples were 98.5% and 97% after 60th cycle respectively. The enhanced electrochemical performance is attributed to fine and amorphous Si based nanocomposite obtained through HEMM process.