We report on the synthesis of poly(vinyl alcohol) (PVA)-silica hybrid nanofibers via sol-gel electrospinning. Silica is synthesized through acid catalysis of a silica precursor (tetraethyl orthosilicate (TEOS) in ethanol-water), and fibers are obtained by electrospinning a mixture of the silica precursor solution and aqueous PVA. A systematic investigation on how the amount of TEOS, the silica-PVA ratio, the aging time of the silica precursor mixture, and the solution rheology influence the fiber morphology is undertaken and reveals a composition window in which defect-free hybrid nanofibers with diameters as small as 150 nm are obtained. When soaked overnight in water, the hybrid fibers remain intact, essentially maintaining their morphology, even though PVA is soluble in water. We believe that mixing of the silica precursor and PVA in solution initiates the participation of the silica precursor in cross-linking of PVA so that its -OH group becomes unavailable for hydrogen bonding with water. FTIR analysis of the hybrids confirms the disappearance of the -OH peak typically shown by PVA, while formation of a bond between PVA and silica is indicated by the Si-O-C peak in the spectra of all the hybrids. The ability to form cross-linked nanofibers of PVA using thermally stable and relatively inert silica could broaden the scope of use of these materials in various technologies.