The effect of different oil on morphologies of emulsion electrospun products has been systematically studied. High photocatalytic degradation performed titanium dioxide (TiO2) nanomaterials with diverse morphologies, including nanoparticles, nanofibers, necklace-like nanofibers, porous nanofibers and surface rough nanotubes were prepared based on different water/oil phase separation processes due to distinctive properties of oils. The crystallinity and morphology of as-prepared nanomaterials were characterized by XRD and SEM, the optical absorption property was analyzed by UV Visual spectrophotometer, N-2 adsorption-desorption was carried to measure the micro-structures and pores distribution of obtained nanomaterials. The photocatalytic activities of as fabricated nanostructures were evaluated by the degradation of Rhodamine B (RhB) under illumination of a xenon lamp as light source. The results indicated that the different nanostructure can be obtained easily by changing the types of oil added into electrospun precursor solutions, and photocatalytic studies indicated that almost all of samples prepared by oil added precursors showed improved photocatalytic activities compared with their traditional counterpart. Our systematic study in this work implied that emulsion electrospinning is a simple and feasible method to prepare nanomaterials with diverse morphologies, which can be used in fabricating other semiconductor-based nanomaterials. (C) 2015 Elsevier B.V. All rights reserved.