Changes of crystal structures and microstructures of SiO2 and graphite powder mixtures induced by high-energy milling, the effect of these changes on the reactivity of reactants, and the mechanism of enhanced SiC formation have been studied using a variety of analytical instruments, including X-ray diffractometry, scanning electron microscopy, transmission electron microscopy, solid-state Si-29 nuclear magnetic resonance, and nitrogen adsorption (i.e., the BET method). High-energy milling before carbothermic reduction leads to substantial changes in the structural and energy states of the reactants, which in turn increases the reactivity of the reactants and enhances the formation of nanostructured SiC particles. Furthermore, the structural and energy-state changes contribute to the enhanced SiC formation through the increased reaction kinetics as well as the increased reaction driving force.