Nanocomposites comprising silicon (Si), graphite (C) and single-walled carbon nanotubes (SWNTs), denoted as Si/C/SWNTs, have been synthesized by dispersing SWNTs via high power ultrasonication into a pre-milled Si/C composite mixture, followed by subsequent thermal treatment. The Si/C composite powder was prepared by high-energy mechanical milling (HEMM) of elemental Si and graphite using polymethacrylonitrile (PMAN) as a diffusion barrier suppressing the possible mechanochemical reaction between silicon and graphite to form SiC, and further prevent the amorphization of graphite during extended milling. A nanocomposite with nominal composition of Si-35wt.% SWNTs-37wt.% exhibits a reversible discharge capacity of ∼900mAhg−1 with an excellent capacity retention of capacity loss of 0.3% per cycle up to 30 cycles. Functionalization of the SWNTs with LiOH significantly improves the cyclability of the nanocomposite containing Si-45wt.% SWNTs-28wt.% exhibiting a reversible capacity of 1066mAhg−1 and displaying almost no fade in capacity up to 30 cycles. The improved electrochemical performance is hypothesized to be attributed to the formation of a nanoscale conductive network by the dispersed SWNTs which leads to successful maintenance of good electrical contact between the electrochemically active particles during cycling.