In this work, the authors present a detailed synchrotron radiation photoemission study of the interactions of metallic titanium with dielectric substrates. In particular, the authors focus on the formation of titanium silicide upon deposition when titanium interacts with SiO2 based substrates. Both TiSi and TiSi2 are present, but TiSi2 grows preferentially upon annealing. When deposited on carbon-containing low-k materials, titanium interacts with the surface to form titanium carbide and titanium silicide. At elevated temperature, carbon in the low-k dielectric assists in the conversion of titanium silicide to titanium silicate. Published by the AVS.