A method of forming an SOI substrate comprising a single crystal spinel insulating film and a single crystal silicon film laminated on a single crystal silicon substrate, in this order, wherein after said single crystal insulating film is formed on said single crystal silicon substrate, the surface of said single crystal insulating film is irradiated with an ion beam to smooth the surface and thereafter said single crystal silicon film is formed thereon, said insulating film being irradiated with said ion beam at an incident angle of about 85 degrees or more to the normal direction of the surface, said single crystal silicon substrate with said single crystal insulating film formed thereon being revolved while said insulating film is irradiated with said ion beam.