The electrochemical behaviour of passive film formed on 2205 duplex stainless steel in 0.1 M Na(2)S(2)O(3) solutions was investigated using potentiodynamic polarization, EIS, Mott-Schottky analysis and the compositions of oxide film in different passive regions were carried out by XPS. The results indicated that the impedance is dependent on the applied potential indicating the occurrence of a charge transfer reaction in a porous film. The doping densities evaluated from Mott-Schottky plots demonstrated that there existence of two donor levels in the space charge layer of the passive films. The donor density (N(D1) and N(D2)) values are in the range of 10(20)-10(21) cm(3), and decreases exponentially with increasing film formation potential, which is in good agreement with the theoretical consequences of the PDM. The polarization curve and XPS results shows that in the passive regions the 2205 duplex stainless steel exhibits different electrochemical and semiconductor properties. (C) 2011 Elsevier B.V. All rights reserved.