Small/Wide Angle X-ray Scattering (S/WAXS) is commonly applied to study the hierarchical structure of cellulosic materials. This structural information, such as the crystallinity index and the degree of cellulose fibril orientation, is essential for a fundamental understanding of the mechanical properties of cellulosic biomaterials. In addition, S/WAXS using synchrotron-based μXRD links the atomic and nanoscale structure to the microscopic structure by raster scanning samples with a μ-focused X-ray beam, which reveals local structural variations related with micro-morphology.Here, we present scanning μXRD applied to regenerated cellulose fibers and cellulosic biocomposite films. Compared to regular XRD with macroscopic beam sizes, μXRD allows the mapping of S/WAXS signal of cellulose nanofibrils within the a single regenerated cellulose fiber. The morphology of nanofibrils determined by SAXS further help resolve the atomic structure through fitting the WAXS data. For cellulosic biocomposites, μXRD identifies different material phases within the composites. By determining the cellulose microfibril angle, the scanning image can further reveal wood cell aggregations formed during the hot-press process with PCL.These examples demonstrate that scanning μXRD is a powerful technique for characterizing both hierarchical structures and structural variations with high spatial resolution in real space for