The interaction of ammonium hydroxide (NH4OH) with zircaloy-4 (Zry-4) was investigated using X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) methods. In order to study the surface chemistry of NH4OH/Zry-4 system, the binding energies of N1s, O1s and Zr3d electrons were monitored. The N1s peak intensity was remarkably increased by following cycles of Ar+ sputtering of NH4OH dosed Zry-4 surface at room temperature. Because the nitrogen stayed under the subsurface region was diffused out onto the Zry-4 surface after oxygen concentration was decreased. These could be occurred after the surface oxygen was diffused into the bulk or desorbed out from the surface until Ar+ fluence was 6.0 × 1016 Ar+/cm2 then the surface was relatively atomic deficient state. The O1s peak intensity was decreased by stepwise Ar+ sputtering. After many cycles of Ar+ sputtering, the peak intensities of Zr3d peaks did not change much but the shape of the peak clearly did change. This implies that the oxidation state of zirconium was changed during stepwise Ar+ sputtering of NH4OH/Zry-4. The Zr3d peak intensity of zirconium nitride (ZrNx) increased as the intensity of N1s (from zirconium nitride) increased but the Zr3d peak intensity of zirconium oxide (ZrOx) decreased due to the depopulation of the oxygen species on the surface region. We also observed that the peak intensity of Zr4+ was nearly same after Ar+ sputtering processes but the peak intensity of metallic zirconium increased compared to that of before the sputtering process was performed.