The interface stability of Zr-based high-k dielectrics with an oxide buffer layer was explored with x-ray (hυ=1254 eV) and ultraviolet (hυ=21.2 eV) photoemission spectroscopy. Zirconium oxide films were grown and characterized in situ in a stepwise sequence to explore their chemical stability and electronic properties as a function of film thickness and processing conditions. The buffer layers serve to lower the interface state density and to address the high temperature instabilities of ZrO2 in direct contact with Si. This research addresses three issues: (1) the development of the band offsets and electronic structure during the low temperature (T≪300°C) growth processes, (2) variations in the band structure as effected by process conditions and annealing (T≪700°C), and (3) the interface stability of Zr oxide films at high temperatures (T≫700°C). Annealing the as-grown films to 600°C results in an ∼2 eV shift of the ZrO2-Si band alignment, giving a band offset that is, favorable to devices, in agreement with predictions and in agreement with other experiments. We propose that the as-grown films contain excess oxygen resulting in a charge transfer from the Si substrate to the internal (ZrO2-SiO2) interface and that annealing to 600°C is sufficient to drive off this oxygen. Fu- rther annealing to 900°C, in the presence of excess Si at the surface, results in decomposition of the oxide to form ZrSi2.