TiO2 nanofibers with special thorny morphology were successfully synthesized by the combination of electrospinning and silica etching technique. This elaborate TiO2 nanostructures exhibited super-high specific surface area (329.7 m(2) g(-1)), which was nearly 13 times higher than that of primary electrospun TiO2 nanofibers (25.6 m(2) g(-1)). The morphological, component, structural and optical properties were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectrum (EDS), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectra (XPS) and UV-visible (UV-vis) diffused reflectance spectroscopy (DRS). Compared with the pristine electrospun TiO2 and SiO2/TiO2 nanofibers, the thorny TiO2 nanofibers not only possessed improved photocatalytic efficiency in photodegradation of Rhodamine B (RhB), but also showed higher specific capacitance in the supercapacitor applications. These results suggest that the thorny TiO2 nanofibers with super large specific surface area exhibit potential applications in both photocatalysis and supercapacitor fields. (C) 2015 Published by Elsevier B.V.