ABSTRACT:With the recent development of an X-ray source, focusing optics, and X-ray detectors, microbeam Xray scattering techniques have been well established and widely applied to the characterization of polymeric materials. Microbeam X-ray scattering is a unique and powerful tool that provides abundant information on local structures, such as the spatial inhomogeneity of materials and the structural change at a local position. Furthermore, by combining microbeam small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS), the observable spatial scale range is from several to several hundred Å , which is the most important scale range in the hierarchical structure analyses of polymers. In this review, the representative applications of microbeam X-ray scattering to polymer crystallization, spatial inhomogeneity analyses, stress transfer under external field and the microphase separated structure analyses in block copolymer systems are introduced. [doi:10.1295/polymj.PJ2007077] KEY WORDS Microbeam Small-and Wide-angle X-ray Scattering / Polymer Characterization / X-Ray scattering techniques are widely applied to the observation of various polymer structures. X-Ray scattering is mainly classified into small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS), depending on the scattering angle. As is easily understood by using the Bragg formula ( ¼ 2d sin ), when the scattering angle 2 decreases, scattering reflects a large structure. SAXS, which is X-ray scattering at small angle (< 2, 3) region, provides information on nanostructures in a size range of several to several ten nanometers. In the field of polymeric materials, SAXS is typically applied to obtaining information on crystalline lamella stacking structures, 1,2 various microphase separated structures in block copolymer systems, 3,4 and organic-inorganic composite structures. 5,6 On the other hand, WAXS is typically applied to obtaining information on sub-nanometerscale structures, such as crystal packing and amorphous structures.To determine the structural characteristics of polymeric materials in detail, it is also very important to understand the formation and/or deformation mechanisms of such materials. Although X-ray scattering experiments were limited to the static measurements in laboratory X-ray sources until early 1980s, the advent of a synchrotron X-ray source and the development of X-ray detectors 7-13 have enabled us to observe a one-or two-dimensional scattering pattern within a second, making it possible to perform timeresolved X-ray scattering measurements for various structural changes, such as crystallization, 14-17 structural changes due to deformation [18][19][20][21][22][23] and phase transition due to temperature change. [24][25][26] While many polymeric materials exhibit spatial inhomogeneity on a micrometer scale, conventional X-ray scattering techniques provide the information that is spatially averaged over more than hundreds micrometer of the sample area irradiated by X-ray beam. Structural inmhom...