Both C54 and C49 structure TiSi2 were found to grow epitaxially on (111)Si. Epitaxial regions, as large as 15 μm in size, were observed. The orientation relationships between epitaxial C54‐TiSi2 and Si were determined to be TiSi2//Si, (004)TiSi2//(022)Si or TiSi2//Si, and (400)TiSi2//(022)Si, whereas those between C49‐TiSi2 and Si are TiSi2//Si and (130)TiSi2//(111)Si. Interfacial dislocations were identified to be of mixed type with (1)/(6) 〈112〉 Burgers vectors. The dislocation spacings were found to vary from 170 to 600 Å. Polytype structures with different spacings were observed by the lattice imaging method. The growth of the most conductive silicide epitaxially on silicon presents an exciting possibility to fabricate novel high‐speed devices.