Core-shelled SiC–SiO2 nanowires have been synthesized on mechanically scratched Si substrates using a catalyst-assisted chemical vapor reaction process at 1100°C. The average diameter and length are 30 nm and in the order of 101 μm, respectively. The SiC core exhibits a single crystalline structure, while the core is amorphous. High-resolution transmission electron microscopy images and selected area diffraction patterns show that the (111) planes of the SiC are at an angle of approximately 71° to the nanowires axis. The existence of the SiO2 alters the cathodoluminescence spectra of the SiC nanowires. A growth mechanism is also suggested.