Growth conditions and structural properties of vacuumevaporated fluoride films on Si(lll) and (100) substrates are reviewed. It has been found that single crystal CaF2 films are grown on both (111) and (100) substrates at temperatures of 600–800°C and 500–600°C, respectively. It has also been found that SrF2 and BaF2 films of good crystalline quality are grown on Si(lll) at temperatures around 600°C, but that the films grown on Si(100) contain (111) oriented crystallites. In epitaxial growth of a Si/CaF2/Si structure, a novel growth method is presented, in which a thin Si layer is deposited at room temperature prior to deposition of a thick Si film at elevated temperature. Investigations on growth of mixed fluoride films, radiation damage in CaF2 films, and epitaxial relations in the fluoride/Si heterostructures are also presented.