The catalyst-free synthesis of silicon carbide (SiC) nanowires was carried out from polyvinyl alcohol (PVA)/silica electrospun nanofibers at high temperature. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray powder diffraction (XRD), and thermogravimetery analysis (TGA) were employed to study morphology and formation of SiC nanowires. Based on the TGA analysis, the carbon yield was increased when inert gas flow rate and heating rate decreased and polymeric nanofibers has been stabilized. The XRD and TEM results showed that the produced nanowires were crystalline beta-SiC and rather homogeneous in thickness with an average diameter around 50 to 70 nm and a length of more than 10 mu m. Finally, a possible growth mechanism of beta-SiC nanowire based on a vapor-solid (VS) mechanism was proposed.