In this study, TiO2 nanofibers with a high aspect ratio and a large specific surface area were synthesized using the electrospinning technique, and the effect of calcination temperature on their crystal structure, diameter, specific surface area and photocatalytic activity was systematically investigated. The electrospun, as-prepared PVP/TTIP nanofibers were several tens of micrometers in length with a diameter of 74 nm. TiO2 nanofibers with an average diameter of 50 nm were prepared after calcination at various temperatures. The calcination temperature significantly influenced the photocatalytic and material properties of TiO2 including grain size and specific surface area. When compared to other nanostructured TiO2 materials, such as commercial TiO2 nanoparticles (P25, Degussa), the TiO2 nanofibers exhibited greater photocatalytic activity for the degradation of acetaldehyde and ammonia.