Rapid thermal vacuum processing (RTVP) has been employed to form silicides of titanium on both single and polycrystalline silicon. Resistivity values as low as 13 μΩ cm were obtained for reaction temperatures in the range 600–900 °C for various times (≤30 s). For the lower temperature (600 °C) the conversion to TiSi2 was observed through both physical (Rutherford backscattering) and electrical (four-point-probe) techniques. The native oxide of silicon was also seen to be broken up by the thermal treatment and the oxide moving to the surface to form a stable thin TiO2 surface layer. Unlike previous reports of the formation of titanium silicides in gas we have observed a clean sharp silicon-silicide interface.