Polycrystalline mixed-phase TiO2 nanofibers embedded with 2.0% w/v Ag nanoparticles was prepared by the electrospinning technique. Calcination of dry Ag nanoparticles-titanium (IV) isopropoxide/PVP electrospun nanofiber mats in air at 510∘C for 24 h yielded polycrystalline TiO2/Ag nanofibers. The morphology and distribution of silver nanoparticles were observed by transmission electron microscopy (TEM), scanning TEM (STEM), and high-angle annular dark-field (HAADF) imaging. Mixed-phase anatase and rutile TiO2 nanofibers were produced with Ag nanoparticles. High-resolution TEM lattice-fringe measurements showed good agreement with Ag (111), anatase (101), and rutile (110) phases. The photocatalytic activity of TiO2/Ag nanofibers was compared to the photocatalytic activity of pure TiO2 nanofibers by studying the photodegradation of methyl red dye under UV light irradiation, in a photoreactor. UV-visible absorbance spectra showed that the rate of decay of the dye in case of photodegradation by TiO2/Ag nanofibers was 10.3 times higher than that by pure TiO2 nanofibers. The retaining of the fiber morphology along with the increased surface area due to the addition of Ag nanoparticles can be believed to enhance the photocatalytic oxidation of methyl red dye.