The oxidation of NiAl(110) was investigated in the temperature regime between 300K and 1300 K using LEED (low energy electron diffraction), TPD (temperature programmed desorption) and HREELS (high resolution electron energy loss spectroscopy). The adsorption of N2O and O2 up to reconstructions. Stepwise annealing of the oxygen-saturated sample from 600 K to 1300K in UHV (ultra-high vacuum,) results in firstly the onset of randomly oriented then finally fairly well-ordered. 5 ${AA}$ Al2O3 film with quasi-hexagonal periodicity. Ordered thicker oxide films of 18-30 ${AA}$ seem to be grown on this interfacial oxide layer by direct oxidation of sample at elevated temperature between 1150 and 1300 K because of the LEED pattern consisting of new broad hexagonal spots and the previous 5 ${AA}$ spots. Although the periodicity of surface oxygen arrays shows no significant change from an hexagonal close-packing, the O-O distance changes from ∼3.0 ${AA}$ film to ∼2.9 ${AA}$ for thicker oxides. with the appearance of Auger parameter, for the 5${AA}$ film can be described better as an interfacial oxide layer. The observation of three symmetric phonon peaks can be also a supporting evidence for this phase assignment since thicker oxide films on the Same Ni2Al3(110) show somewhat different phonon structure much closer to that of the ${gamma}$-Al2O3. The adsorption/desorption of methanol further proves the preparation of less-defective and/or oxygen-terminated Al2O3 films showing ordered phase transitions with the change of oxide thickness between 5 ${AA}$ to 30 ${AA}$.