The effect of interfacial oxynitride layer on the band alignment and thermal stability of amorphous LaAlO3∕Si0.75Ge0.25 heterojunction has been investigated. The presence of interfacial oxynitride layer shifts the band alignment due to the modification of interfacial dipole. During the thermal annealing, it was found that the interfacial electronic structures were altered, and the valence-band maximum of LaAlO3 films shifted to the lower energy due to the diffusion of nitrogen species from the interfaces into LaAlO3 films at high annealing temperature.