Orientation of cellulose nanowhiskers (CNWs) derived from tunicates, in an all-cellulose nanocomposite, is achieved through the application of a magnetic field. CNWs are incorporated into a dissolved cellulose matrix system and during solvent casting of the nanocomposite a magnetic field is applied to induce their alignment. Unoriented CNW samples, without the presence of a magnetic field, are also produced. The CNWs are found to orient under the action of the magnetic field, leading to enhanced stiffness and strength of the composites, but not to the level that is theoretically predicted for a fully aligned system. Lowering the volume fraction of the CNWs is shown to allow them to orient more readily in the magnetic field, leading to larger relative increases in the mechanical properties. It is shown, using polarized light microscopy, that the all-cellulose composites have a domain structure, with some domains showing pronounced orientation of CNWs and others where no preferred orientation occurs. Raman spectroscopy is used to both follow the position of bands located at ∼1095 and ∼895 cm -1 with deformation and also their intensity as a function rotation angle of the specimens. It is shown that these approaches give valuable independent information on the respective molecular deformation and orientation of the CNWs, and the molecules in the matrix phase, in oriented and nonoriented domains of all-cellulose composites. These data are then related to an increase in the level of molecular deformation in the axial direction, as revealed by the Raman technique. Little orientation of the matrix phase is observed under the action of the magnetic field indicating the dominance of the stiff CNWs in governing mechanical properties. © 2012 American Chemical Society.