We demonstrate that the addition of a molybdenum interlayer between titanium and silicon enhances the formation of C54 TiSi2, without bypassing the formation of the C49 TiSi2 phase. In situ x-ray diffraction analysis during rapid thermal annealing, at a rate of 3 °C/s, was used to study the phase formation sequence of TiSi2 starting from a blanket bilayer of Ti on Mo on a polycrystalline Si substrate. It was shown, as in the case without the Mo layer, that the C49 TiSi2 phase forms first, followed by the C54 TiSi2 phase. The results were similar for undoped or arsenic, boron, and phosphorous doped polycrystalline silicon substrates. The temperature range over which the C49 phase is stable is reduced, on average, by 80 °C. The lower end of the range (appearance of C49) is increased by approximately 60 °C and the upper end of the range (disappearance of C49) is decreased by about 20 0C. The orientation of the C49 phase differs in that both the C49(131) and C49(060) orientations are observed, compared to the case without the Mo layer where only the C49(131) orientation is observed.