Polyvinyl acetate (PVAc)/titanium dioxide (TiO2) hybrid nanofibers were fabricated by combining sol–gel process with electrospinning technology, which consisted of PVAc as organic segment and TiO2 as inorganic part. The surface structures of the PVAc/TiO2 hybrid nanofibrous mats were examined using scanning electron microscopy (SEM). The surface morphology and bulk structures of single nanofiber were investigated by atomic force microscopy (AFM) and transmission electron microscopy (TEM). Fourier transform infrared spectroscopy (FTIR) was employed to analyze the chemical structures of the PVAc/TiO2 hybrid nanofibers. SEM scanning revealed that the fibrous structure was formed. AFM observations presented a significant difference in the morphology of the nanofibers before and after hybridization. It was observed from TEM images that some black streaks with various lengths distributed in a nanofiber. The FTIR analysis indicated the newly formed associated hydrogen bond because of the hybrid effect between PVAc and TiO2 sol.