Highly ordered TiO2 nanotube arrays (TNAs) were prepared by anodization, and followed by annealing in the atmospheres of Air, Vacuum, Ar, and H-2. The effect of annealing atmosphere on the crystal structure, composition, and electronic properties of TNAs were systematically investigated. Raman and EDS results indicated that the TNAs annealed in anaerobic atmospheres contained more oxygen vacancies, which result in the substantially improved electron transport properties and reduced work function. Moreover, it was found that the FE properties of TNAs were highly dependent on the annealing atmosphere. By engineering the annealing atmosphere, the turn-on field as low as 2.44 V/mu m can be obtained from TNAs annealed in H-2, which was much lower than the value of 18.23 V/mu m from the TNAs annealed in the commonly used atmosphere of Air. Our work suggests an instructive and attractive way to fabricate high performance TNAs field emitters. (C) 2015 Elsevier Ltd. All rights reserved.