Nanocomposites of Si/C were synthesized from Si and polystyrene (PS) resin using high-energy mechanical milling (HEMM) followed by subsequent heat-treatment. The resultant nanocomposites are comprised of amorphous carbon and nanocrystalline silicon as verified by X-ray diffraction (XRD). The XRD results also indicate the presence of iron silicide (FeSi) arising as a contaminant during HEMM. The Si/C nanocomposite corresponding to Si:C = 1:2 composition obtained after milling in two stages of 12h each for a total time period of 24h shows a capacity as high as ∼850mAh/g with reasonable capacity retention (∼1.1% loss/cycle). The increase in either heat-treatment temperature or milling time renders the nanocomposites more stable at the expense of capacity. Transmission electron microscopy (TEM) analysis shows that the HEMM derived Si nanocrystallites <50nm in size are distributed homogeneously within the amorphous carbon matrix.