Submicron scale vanadia/silica hybrid nanofiber mats have been produced by electrospinning silica sol-gel precursor containing vanadium oxytriisopropoxide (VOTIP), followed by calcinations at high temperature. The properties of the resulting inorganic hybrid nanofiber mats are compared to those of electrospun pure silica nanofibers. SEM images show fibers are submicron in diameter and their morphology is maintained after calcination. Physisorption experiments reveal that silica nanofiber mats have a high specific surface area of 63m(2)/g. FT-IR spectra exhibit Si-O vibrations and indicate the presence of V(2)O(5) in the fibers. XPS studies reveal that the ratio of Si to O is close to 0.5 on the surface of fibers and the amount of vanadium on the surface of fibers increases with calcination. XRD diffraction patterns show that silica nanofibers are amorphous and orthorhombic V(2)O(5) crystals have formed after calcination. EFTEM images demonstrate the growth of crystals on the surface of fibers containing vanadium after calcination. SEM images of fibers with high-vanadium content ( 50 mol% V : Si) show that vanadia crystals are mostly aligned along the fiber axis. XPS shows an increase in vanadium contents at the surface, and XRD patterns exhibit an increase in the degree of crystallinity. A coaxial electrospinning scheme has successfully been employed to selectively place V(2)O(5) in the skin layer. Copyright (c) 2006.