Silicon nanoparticles have been synthesised using mechanochemical ball milling and an inert salt buffer to limit the growth and control the size of the Si particles produced. The solid–liquid metathesis reaction used silicon tetrachloride and lithium with LiCl as the buffer to generate Si nanoparticles. Once the LiCl was removed, X-ray amorphous Si was identified using electron energy loss spectra, at 99 eV and energy filtered transmission electron microscopy. The morphological analysis showed spherical like particles with an average size between 10–30 nm depending on the amount of salt buffer phase added to the reactants. This synthesis method can be used to produce very small Si particles in tuneable sizes for a wide range of applications.