The effects of vacuum and inert gas annealing of ultra-thin (20Å) CVD Ta2O5 films deposited on Si substrates, with and without oxynitride interface layer, on the Ta2O5/Si interface stability were examined extensively by means of in-situ X-ray Photoelectron Spectroscopy (XPS), ex-situ Time-of-Flight Secondary Ion mass Spectrometry (ToF-SIMS), and Temperature Programmed Reaction (TPR). When annealed to 680 °C for up to 50 min, changes in ∼ 20Å Ta2O5 films formed on Si(100) are negligible, but annealing to 820 °C for 10 min in vacuum, Ar or N2 produces major chemical restructuring. SiO is formed at the Ta2O5 - Si(100) interfaces and becomes incorporated into the tantalum oxide. A reduced form of Ta, attributed to TaSix, forms at the buried interface. Extending the annealing time to 20 min produces no further changes. SiO desorbs during annealing at 1000 °C. Nitriding Si prior to forming the Ta2O5 film deposition inhibits these processes.