In this study, nanobranched TiO2 nanofibers and silver loaded nanobranched TiO2 nanofibers were prepared by electrospinning technique followed by TiCl4 aqueous solution treatment and silver photodeposition method. Field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) were employed to investigate the morphology of the products. X-ray diffractometer (XRD) and X-ray photoelectron spectroscopy (XPS) were conducted on the samples to study their chemical composition as well as crystallographic structure. The photocatalytic activities of these produced nanofibers were examined with two organic dyes, methylene blue and methyl orange, under ultraviolet (UV) light irradiation. The effect of nanobranches and silver modification on TiO2 nanofibers was revealed in the photocatalysis process. The photocatalytic degradation rates of silver loaded on nanobranched TiO2 nanofibers were 1.6 and 1.7 times as that of pure TiO2 nanofibers in the presence of methylene blue and methyl orange, respectively, which indicated silver nanoparticles combined nanobranches modified on the surface of TiO2 nanofibers could enhance the photocatalytic ability.