To obtain a TiO2 photocatalyst with high photocatalytic efficiency under visible irradiation and good reusability, the Fe3+ and N co-doped TiO2 micro/nano fiber films were fabricated by electrospinning and calcinations. The morphologies and structures of the resulting samples were analyzed by scanning electron microscopy (SEM), x-ray diffraction and x-ray energy dispersion spectroscopy (EDS). The absorbance and chemical oxygen demand (COD) were characterized respectively by UV–visible spectrophotometer and COD Rapid Tester. The results show that the Fe3+ and N co-doped TiO2 micro/nano fiber had a multi-porous structure with an average diameter of about 45 to 506 nm. The crystalinity degrees, visible light absorption of these films were affected by the dosage of Fe3+ and N co-doping (DFN). Moreover, these films exhibited high photocatalytic activity for the degradation of dye waste water under sunlight and it was related to DFN. As DFN was 0.5 %, it has highest crystalinity degree, largest visible light absorption and highest photocatalytic efficiency on dye waste water. The decolor rate of the dye waste water was as high as 67.6 % and its COD decreased from 2800±200 to 236.40 ± 15.61, when the photocatalytic time was only 3 h.