Multi-walled carbon nanotube (MWCNT)/silicon nanocomposites obtained by a grafting technique using the diazonium chemistry are used to prepare silicon negative electrodes for lithium-ion batteries. The covalent bonding of the two compounds is obtained via mono-and multi-layers of phenyl bridges, leading to an ideal dispersion of MWCNTs and silicon nanoparticles that are bound together. The presence of MWCNTs close to silicon nanoparticles enhances the electronic pathway to the active material particles and probably helps to prevent silicon decrepitation upon repeated lithium insertion/extraction by improving the mechanical stability of the electrode at a nanoscale level. This effect results in the enhancement of cycling ability and capacity, which are demonstrated by comparing the nanocomposite electrode to a simple mixture of the two compounds. This technique can be applied to other carbon conductive additives together with silicon or other nanosized active compounds.