Mixed phase TiO2 and Ce-doped TiO2 nanofibers with different content (0.5, 2.0, 8.0%) of cerium ions were prepared by a sol-gel electro-spinning method. Results from SEM showed no beads on the undoped-TiO2 and Ce-doped TiO2 nanofibers with diameters in the range of 77-130 nm. TEM images exhibited that the undoped TiO2 crystallite size on the fiber was bigger than those on the Ce-doped samples. XRD and Ti K-edge XANES were used to determine anatase/rutile phase ratios in pure TiO2 nanofibers, whereas only XANES was used to characterize the anatase/rutile phase ratios in the Ce-doped TiO2 samples. Ce L 3-edge XANES exhibited peak associated with Ce+3 (5727 eV.) in addition to Ce+4 (5731 and 5738 eV.). Samples with the lowest Ce content had the greatest fraction of Ce ions in the Ce+3 state. The photocatalytic activity of the prepared nanofibers was observed by degradation of Rhodamine B under visible light, and the fiber of 0.5 % Ce-doped TiO2 exhibited the highest activity.