Mott-Schottky and photoelectrochemical measurements were used to explore the effects of hydrogen and chloride ions on the electronic properties of the passive film on X70 micro-alloyed steel in a solution of 0.5 M NaHCO3. Mott-Schottky analyses have shown that hydrogen increases the capacitance and donor density, and decreases the flat band potential and the space charge layer thickness of the passive film. The photocurrent of the film is remarkably increased by hydrogen. The effects of hydrogen become more pronounced with an increase in the hydrogen charging current densities. Hydrogen has no noticeable effect on the band gap energy E-g and the process by which hole-electron pairs are photo-generated in the film. The presence of chloride ions in the solution produces some similar effects on the electronic properties of the passive film to those observed with hydrogen, but reduces the photocurrent and increases the band gap energy of the film. No significant synergistic effects on the electronic properties of the passive film were observed in the presence of hydrogen and Cl-. These results provide very useful information for elucidating the mechanism by which hydrogen changes the properties of passive film and then promotes localized corrosion. (C) 2004 Elsevier B.V. All rights reserved.