The surface chemistry of D2O dosed Zircaloy-4 (Zry-4) surface followed by Ar-ion bombardment and annealing was studied by means of X-ray photoelectron spectroscopy (XPS) and Ultraviolet photoelectron spectroscopy (UPS). In the XPS study, Ar-ion bombardment caused decrease of the oxygen on the surface region of Zry-4 and therefore led to change the oxidation states of the zirconium from oxide to metallic form. In addition, oxidation states of zirconium were changed to lower oxidation states of zirconium due to depopulation of oxygen on the surface region by annealing. Up to about 787 K, the bulk oxygen diffused out to the subsurface region and after this temperature, the oxygen on the surface of Zry-4 was depopulated. UPS study showed that the valence band spectrum of the D2O exposed Zry-4 exhibited a dominant peak at around 13 eV and no clear Fermi edge was detected. After stepwise Ar+ sputtering processes, the decrease of the oxygen on the surface of Zry-4 led to suppress the dominant peak around 13 eV, the peak around 9 eV and develop a new peak of the metallic Zr 4d state (20.5-21.0 eV) at the Fermi level.