Surface superstructures (reconstructed structures) have been observed by many techniques. However, it has not been easy to confirm that a superstructure does exist at an interface between two solid layers. The article reports superstructures at semiconductor interfaces studied by a grazing incidence X-ray diffraction technique with use of synchrotron radiation. At metal-semiconductor interfaces, different superstructures give different Schottky-barrier-height values. Superstructures are also found to exist at insulator-semiconductor interfaces fabricated by the metalorgamc chemical vapor deposition (MOCVD) method. In addition, a boron-induced superstructure is found to exist even at the interface between an epitaxial Si layer and a Si (111) substrate.