Flexible N-doped TiO2/Cultrafine fiber (NTCf) mat has been produced via electrospinning and subsequent heat treatment, analyzed by a combination of characterizations. The nitrogen content can be modulated by the addition of urea. The composite fiber with mean diameter of around 500 nm exhibits outstanding mechanical flexibility. The TiO2 in the fiber obtained at 700 degrees C is anatase with a mass ratio of 23 wt%. In the photodegradation experiment under simulated sunlight, the as-prepared flexible mat demonstrates remarkable efficiency in the degradation of methylene blue (MB) due to the well-proportioned distribution of TiO2 nanoparticles and the improvement of charge transfer process. The nitrogen species in TiO2 lattice and the nitrogen functional groups on the surface of the fiber play crucial impacts on the photocatalytic activity. (C) 2014 Elsevier B. V. All rights reserved.