Physical properties of polymer materials are deeply related to not only the primary structure but also the higher ordered structure such as periodic structures and molecular orientation. If the target material consists of ordered and non-ordered region, the former structure can be selectively detected by X-ray scattering method, whereas structural information of both the regions is obtained by infrared absorption spectroscopy. Particularly for thin film materials, infrared pMAIRS (p-polarized multiple-angle incidence resolution spectroscopy) and GI-XRD (grazing incidence X-ray diffraction methods are very useful for precise structural analyses.