In order to solve the complex spinneret and unstable structure of multifludic electrospinning and side-by-side electrospinning, TiO2 nanofibers with hierarchical porosity were fabricated via microemulsion electrospinning, which can be realized just by single-spinneret electrospinning. The morphology, crystal, and specific surface area of the TiO2 nanofibers were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), and physisorption analyzer. The photocatalytic activities of TiO2 nanofibers calcined at 500, 700, and 900 degrees C were examined. The experimental results indicated that TiO2 nanofibers were hollow, and the wall of nanofibers possessed abundant mesopores. The specific surface area of TiO2 nanofibers calcined at 500 degrees C was approximately 41.4 m(2)/g, which was favorable for increasing the photocatalytic reaction sites and the separation efficiency of electron-holes. The photocatalytic results demonstrated that compared with solid TiO2 nanofibers, the photo catalytic activities of the TiO2 nanofibers prepared via microemulsion electrospinning were significantly enhanced. Particularly, the TiO2 nanofibers calcined at 500 degrees C could decompose methyl blue (MB) solution completely within 70 min. The results verified that microemulsion electrospinning was indeed a simple, versatile, and convenient method to prepare porous inorganic nanofibers for various applications.