A mechanochemical method for the simultaneous one-step production and functionalization of silicon nanoparticles is presented. Fresh surface created through mechanical attrition of the silicon during high energy ball milling (HEBM) allows for direct reaction between the silicon and the reactive alkene or alkyne media, resulting in a covalent linkage. The resulting nanoparticles exhibit strong blue luminescence, indicative of small nanoparticle sizes and a functionalized surface.