C49‐TiSi2 film was grown epitaxially on Si(111) substrate by depositing Ti film on Si(111)‐ 7×7 surface followed by in situ annealing in ultrahigh vacuum. The deposition was monitored by means of reflection high energy electron diffraction as a function of the thickness of Ti film. The best result for the growth of epitaxial C49‐TiSi2 was obtained from the Ti(30 ML)/Si(111)‐7×7 sample which was annealed at 650 °C for 20 min. Images of cross‐sectional high resolution transmission electron microscopy shows that the silicide/silicon interface is shown to be clear and flat. The orientation relationships are TiSi2[2¯11]‖Si[011¯], TiSi2 (120)‖Si(111) without misorientation angle. Almost the whole area of the TiSi2 layer is revealed as an epitaxial C49 structure.