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This paper reports the oxidation mechanism of epitaxial Ni thin films grown on GaN/sapphire(0001) substrates, investigated by real-time x-ray diffraction and scanning electron microscopy. At the initial stage of oxidation process, a thin NiO layer with a thickness of ~50Å was formed on top of the Ni films. The growth of such NiO layer was saturated and then served as a passive oxide layer for the further oxidation process. For the second oxidation stage, host Ni atoms diffused out to the surfaces of initially formed NiO layer through the defects running vertically to form NiO grains, while the sites that were occupied by host Ni, became voids. The crystallographic properties of resultant NiO films, such as grain size and mosaic distribution, rely highly on the oxidation temperatures.