Titania nanotube was prepared by two-step anodization process, and compared morphology features and photoelectrocatalytic activity of TNT fabricated by one-step anodization process. The results suggested that TNT fabricated by two-step anodization processes exhibited bigger difference in morphology features in comparison with TNT prepared by one-step anodization process. The average tube length and diameter of TNT fabricated by two-step anodization processes displayed a little increase than those of TNT fabricated by one-step anodization process, and were 7.67μm and 72.12nm respectively. The wall thickness decreased to 16.36nm, which resulted in increase of aspect ratio from 59.73to 104.83. Correspondingly, the photon-to-hydrogen conversion efficiency significantly increased from 0.14% to 0.36%. Moreover, the presence of ethylene glycol as target pollutant further enhanced the photoelectrocatalytic activity of pollutant degradation and hydrogen generation of TNT. Thus, two-step anodization processes is a simple and effective method to improve the morphology features and photoelectrocatalytic performance of TNT and have an application prospect in photoelectrocatalytic degradation of organic pollutants and simultaneous hydrogen generation.