The objective of this work is to investigate interface chemistries which minimize the interfacial silicon oxide transition region at Si/high-k dielectric interfaces. We report on the mechanism by which a silicon native oxide layer is converted into magnesium silicate. The deposition of metal Mg onto a SiO 2 native oxide surface resulted in the formation of a magnesium silicide in addition to substochiometric silicon oxides and a significant decrease in the oxidised silicon signal. Annealing to 300°C resulted in the decomposition of the magnesium silicide, oxidation of the Mg, and the desorption of excess metallic Mg. Subsequent annealing to 500°C resulted in converting the SiO 2 into magnesium silicate. The results suggest that the decomposition of the Mg silicide in the presence of the residual native oxide facilitates silicate formation at 500°C. Due to the reported thermal stability of Mg silicate it is suggested that this process may be beneficial in modifying the interface characteristics of the Si/high-k dielectric interface which has potentially significant implications for future semiconductor device generations.