Two types of square wave anodization (type 1 and type 2) were employed in this work to form a passive film on Ti in a 0.5 M H2SO4 solution. The influences of the anodization potential and duration on the electronic properties and structures of the passive films were studied by Mott-Schottky plots, auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). The results showed that the donor density, N-D, of the passive film decreased and the flat band potential, E-FB, shifted to the positive direction with the increase of the anodization duration and high anodization potential irrespective of whether type 1 or type 2 was used. Moreover, the passive film that formed on Ti using type 1 had a lower donor density and a more positive flat band potential than that on Ti using type 2 at one fixed anodization duration (only exchanging the anodization order of 1 V and the high potential). XPS analysis revealed that the outmost passive film was only composed of TiO2, the inner passive film was mainly composed of TiO2 with some amount of TiO and Ti2O3, and the TiO2 concentration in the outermost passive film increased with the increase of the anodization duration and the high potential in the case of using type 1 or type 2, implying an increased degree of crystallinity. The AES results showed that the O/Ti atomic ratio of the passive film obviously increased with the increasing anodization duration and high potential, demonstrating the increased homogeneous characteristic of the passive film; this was in agreement with the Mott-Schottky and XPS results. (C) 2017 Elsevier B.V. All rights reserved.