We demonstrate the synthesis of hollow silicon carbide nanoparticles via a two-step process involving the non-thermal plasma synthesis of silicon nanoparticles, followed by their in-flight carbonization, also initiated by a non-thermal plasma. Simple geometric considerations associated with the expansion of the silicon lattice upon carbonization, in combination of the spherical geometry of the system, explain the formation of hollow nanostructures. This is in contrast with previous reports that justify the formation of hollow particles by means of out-diffusion of the core element, i.e., by the Kirkendall nanoscale effect. A theoretical analysis of the diffusion kinetics indicates that interaction with the ionized gas induces significant nanoparticle heating, allowing for the fast transport of carbon into the silicon particle and for the subsequent nucleation of the beta-silicon carbide phase. This work confirms the potential of non-thermal plasma processes for the synthesis of nanostructures composed of high-melting point materials, and suggests that such processes can be tuned to achieve morphological control. V C 2015 AIP Publishing LLC.