Composite fibers of polyvinylpirrolidone and titanium propoxide were prepared using the electrospinning technique. Titanium oxide fibers were obtained on heat treatment of this composite. These fibers were characterized by means of specific surface area, thermal analysis, X-ray diffraction and electronic microscopy processes. Evaluation of their photocatalytic activity was carried out in comparison with the nanometric powder TiO2 P25 from Degussa as reference. The photo-oxidative decomposition of methyl orange was followed by ultraviolet-visible spectroscopy to determine the acid- and basic pH values. The heat treatment of these fibers at higher temperatures led to a decrease in the anatase phase responsible for their photoactivity. The heat treatment, the phases of the material, the pH of the medium, and the surface area affected the physical-chemical and photocatalytic properties of the titania fibers.