Mesoporous titanium dioxide (TiO2) hollow nanofibers (HNFs) were successfully prepared by a facile electrospinning and calcination method. Techniques such as X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were utilized to characterize TiO2 fibers. It was revealed that TiO2 crystals with an appropriate anatase fraction (71.58%) were grown and a tubular mesoporous structure was formed with a high specific surface area. Photodecomposition of methyl orange (MO) solution showed that TiO2 HNFs exhibited much higher photocatalytic activity than corresponding TiO2 nanofibers (NFs) and loose-structured nanofibers (LNFs). The significant enhancement of photocatalytic activity was attributed to both the sufficient growth of active anatase phase primarily and a tubular mesoporous nature of TiO2 HNFs.