CuO fibers were successfully fabricated by a simple electrospinning method, followed by calcination. Some experimental parameters such as the content of Cu(NO3)(2)center dot 3H(2)O, the content of PVP, the stirring time, the applied voltage, as well the calcination temperature were investigated, respectively, and their influences on the morphologies of fibers and the spinnability of precursor solution were analyzed. The CuO fibers calcined at 550 degrees C consisted of numerous CuO grains exhibited a well-crystalline structure. Furthermore, the CuO fibers demonstrated effective photo-Fenton degradation to methyl orange with the assist of H2O2 and the adding volume of H2O2 affects the degradation activities greatly. The degradation rate of methyl orange by the CuO fibers in the presence of 238.8 mmol/LH2O2 is 3.8 times as much as one by P25 alone under the irradiation of Xe lamp. The degradation ratio of methyl orange could achieve 83% in 180 min. The enhanced photocatalytic activities of the CuO fibers were attributed to two aspects: one is the well-crystalline of CuO fibers; the other is that H2O2 accepted the photogenerated electrons and holes effectively, which not only prevented the recombination of charge carriers but also produced additional center dot OH. In this work, the formation and photocatalysis mechanisms of CuO fibers were also investigated. (C) 2017 Elsevier B.V. All rights reserved.