In this paper, we proposed the method for profiling of the components of the effective mobility of charge carriers μeff defined by their scattering by surface phonons and by roughness at the film/insulator interfaces. The method is based on the controlled localization of charge carriers relative to the interface under study due to the coupling effect. The proposed method allows us to independently determine mobility components near different interfaces of films. The use of the proposed method for studying the mobility has allowed us to obtain information on the roughness of the interface and on the structural quality of the ultrathin (1–3-nm) layer of Si near the Si/buried oxide interface.