The oriented overgrowth of titanium films obtained by evaporation in an ultrahigh‐vacuum system onto mica was studiedin situby reflection electron diffraction and, after withdrawal from the system, by transmission electron microscopy and diffraction. Films with a thickness of 100 Å or more, prepared on a mica at temperatures of 500°–600°C, are epitaxial single crystals of hexagonal structure; their basal plane is parallel to that of the substrate and the crystallographic axes within the contact planes form an average angle of 30°. These single‐crystal films have a smooth surface and are composed of subgrains rotated around thecaxis with respect to each other, forming angles up to 4°. Films thinner than 100 Å are only partially oriented. Coalescence in these films takes place at a very early stage of growth and continuous films of about 100 Å are obtained, in contrast with the growth of other metals on mica.