The oxygen behavior and its influence on Ti silicide formation is systematically studied in the TiO2/Si and Ti/TiO2/Si systems using Rutherford backscattering, nuclear reaction analysis, and x‐rays diffraction techniques. After annealing in vacuum ( p≪5×10-7 Torr), no reaction was observed up to 900 °C in the TiO2/Si system, whereas in the Ti/TiO2/Si system, metallic titanium reacts with the TiO2 film above 400 °C and at 600 °C a uniform oxygen solid solution is formed. The silicide formation starts at 650 °C and up to 750 °C the only phase formed is Ti5Si3. We found that this phase is kinetically favored as long as the Ti is being supplied by the unreacted film. The growth rate kinetics was found to have parabolic behavior and was therefore controlled by Si volume diffusion. Above 750 °C, TiSi2 forms very rapidly, its growth being nucleation controlled. During the growth of the silicide layer, a diffusion of oxgen toward the surface region was observed. When the oxygen concentration in the surface layer exceeded the solubility limit, Ti oxide precipitated and the silicide growth nearly stopped, even if some silicon reached the surface. At a temperature higher than 850 °C, a marked oxygen loss takes place, most probably via SiO sublimation. The sublimation process is favored by the presence of Si in the surface region and prevents the formation of a stable SiO2 diffusion barrier at the TiSi2/TiOx interface.