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Fluoride ions, which interfere with the oxide formation on zirconium have been over-looked until recently. The effect of fluoride ions on oxide formation and dissolution behaviors in zirconium was investigated in this study. A detailed quantitative characterization of the oxide films formed on Zr702 immersed in a fluorinated nitric acid solution was performed using X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, and representative high-angle annular dark-field scanning Transmission Electron Microscope, (TEM). The corrosion performance in a fluorinated nitric acid solution was discussed. The results reveal that the thickness of the oxide films immersed in the fluorinated nitric acid solution was between 42–48 nm, which is much thinner than that of the oxide layer (~98.85 nm thickness) in the F⁻ free HNO₃ solution. The oxide film was identified to be a nanocrystalline cluster, comprised of outermost HfO₂ and HfF₄ layers, sub-outer ZrO₂ and ZrF₄ layers, and an innermost Zr (F, O)_3.6 layer. This fluoride species penetration through the oxide films indicated that the fluoride ions are responsible for the dissolution of the oxide film of Zr702.