Recently, polymer thin films for use in flexible devices such as semiconductor block copolymers consisting of fully aromatic rigid polymer and rubbery polymer have attracted much attention. Thus, rubbery materials are increasingly being used not only in the amorphous bulk state, but also as ordered thin films (films less than 500 nm in thickness). Additionally, rubber materials are often used as composite materials with inorganic fillers, and thin films on the inorganic substrates are suitable model system for structural evaluation near the interface because of the significantly larger specific area than the bulk material. With this background, precise and rapid methods to evaluate the structures of thin films (periodic order, molecular chain orientation, etc.) are increasingly demanded. In this paper, infrared p-polarized multiple-angle incidence resolved spectroscopy (pMAIRS), and combined methods of pMAIRS with conventional grazing incidence wide-angle X-ray scattering (GI-WAXS) and spectroscopic ellipsometry (SE) methods are introduced for analyses on the hierarchical ordered structure of polymer thin films (crystal, liquid crystal glass, oriented and unoriented amorphous, and their mixed complex structures).