According to the invention, a film of optoelectric single crystal may be formed on a substrate made of optoelectric single crystal by a liquid phase epitaxial process. The process comprises the steps of producing a melt of a solute and a melting medium, a solid phase and a liquid phase coexisting in the melt; then cooling the liquid phase for producing super cooling state in the liquid phase; and contacting the substrate to the liquid phase to form the film on the substrate by an epitaxial growing process. The film may be produced on the substrate, the film having a half value width of an X-ray rocking curve not more than that of the substrate.