We report on the formation of a new material, C40 TiSi2, using pulsed laser annealing. On the basis of this laser-induced C40 TiSi2, the growth of the technologically important C54 phase is significantly promoted and can be accomplished with a subsequent rapid thermal anneal or furnace annealing at temperatures far below that for the normal C54 formation. The undesirable C49 TiSi2 is completely bypassed. C40 TiSi2 can also be easily transformed to the C54 phase with thermal treatments and result in the formation of a pure C54 TiSi2 layer. The synthesis of C40 phase without the additional refractory metals and its promotion effect on the C54 phase formation have great potential for applications in the integrated circuit industry for 0.10 mum technology node and beyond.