Thermal stability of stacked high-κ dielectrics, especially ZrO2, HfO2 and ZrSiO4 /SiO2 layered structures, on silicon has been investigated in terms of ultrahigh vacuum (UHV), 1 Torr N2 and helium (He) gas annealing with controlled oxygen partial pressure (PO2) at 920. Comparison of 2 nm and 20 nm ZrO2 films under UHV annealing revealed that the trigger of silicidation is the contact of ZrO2, SiO and Si accompanying disappearance of interfacial SiO2 layer due to SiO desorption. In the contact position, a small amount of SiO gas can easily change ZrO2 to ZrSi2. This reaction model is also applicable to the silicidation of HfO2 and ZrSiO4, at not only stacked high-κ film/Si substrate interface, but also at gate poly-Si/high-κ film interface. Moreover, comparison of UHV, N2 and He annealing with controlled PO2 revealed that the optimal PO2 ranges in He at which the thermal stability of layered structure can be achieved are wider than those in UHV and N2. This result suggests that He gas physically may obstruct SiO creation due to the quenching of atomic vibration at degradation-prone sites in the SiO2 /Si interface, thus reducing probability of bond breaking process, which is the first step of silicidation.