A novel structure with TiO2 micro-/nano-spheres embedded in nanofibers was fabricated by coaxial electrospinning. The formation mechanism of the embedded structure and the effects of core flow rates on photocatalytic properties were investigated, and their photocatalytic properties were compared with the photocatalytic properties of nano-spheres and nanofibers. The micro-/nano-spheres were embedded in TiO2 nanofibers with different physical properties of core and shell spinning solutions. The specific surface area of the nanofibers improved to 23.852 m(2)/g, and the degradation rate for methylene blue increased to 91.56%. The novel structure has large nanofiber gaps. We obtained a high specific surface area for the micro-/nano-spheres, which present a loose structure and are conducive for UV injection to improve photocatalytic efficiency. (C) 2016 Elsevier Ltd. All rights reserved.