TiO2/polyacrylonitrile (TiO2/PAN) hybrid nanofibers with small TiO2 nanoparticles well-immobilized on the electrospun PAN nanofibers have been successfully fabricated by means of a combination of an electrospinning technique and a hydrothermal process. The as-fabricated hybrid nanofibers were characterized by field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy, X-ray diffraction, and Brunauer-Emmett-Teller analysis. The results revealed that the TiO2/PAN hybrid nanofibers possessed a large surface area as well as being flexible in nature. Such hybrid nanofibers materials have exhibited outstanding performance for the photocatalytic degradation of phenol under UV light irradation. And, by adjusting the operating parameters during the photocatalytic process, the results further showed that the photoreactor pattern, initial pH value and concentration of phenol solution had important influence on phenol degradation. What's more, repeating the experiments five times indicated that the catalyst is stable and recyclable.