Silica nanofibers were developed by a combination of an electrospinning technique and the sol-gel method. In the process, tetraethoxysilane (TEOS), polyvinylpyrrolidone (PVP) and N, N-Dimethylformamide (DMF) were the components of the sol for the production of silica/PVP composite nanofibers by electrospinning. During a thermal treatment, PVP in the hybrid fibers was removed; in this way, we produced ultrafine crystalline silica nanofibers. Scanning electron microscopy, energy dispersive X-ray analyzer, X-ray diffraction, and Fourier transform infrared spectroscopy were used to characterize the nanofibers. These silica nanofibers should be potentially useful in catalyst support, adsorbent, energy storage, and gas storage applications.