We presented a straightforward method to fabricate porous inorganic SiO 2 nanofibrous membrane by one-step calcination of electrospun nanofibers, which encapsulated with carbon nanospheres as template for nanopore generation. The structure, morphology, and composition of the as-spun fibers (PVA/SiO 2 /C) and porous SiO 2 were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The detective results indicated that the carbon nanospheres were uniformly encapsulated inside the PVA/SiO 2 /C nanofibers. After calcination, PVA polymer was removed and high flexible inorganic nanofibrous membrane composed of amorphous SiO 2 was obtained. Simultaneously, carbon nanosphere template was decomposed and uniform nanopores were generated inside the SiO 2 nanofibers. This new method is simple and of low cost and hence is suitable to prepare other porous inorganic nanofibers with high surface area for practical application.