Regenerated cellulose fibers have been considered as potential precursor fibers for carbon fibers because of their balanced cost and performance. Increased attention has been paid to blending lignin with the regenerated cellulose to generate precursor fibers which render good mechanical properties and higher carbon yield. The mechanical properties of carbon fibers have been found closely correlated to the structure of precursor fibers. However, the effects of lignin blending on molecular- and morphological structure of the precursor are still unclear. This study aims at clarifying the structural information of lignin–cellulose precursor fibers from molecular level to mesoscale by scanning X-ray microdiffraction. We present the existence of a skin–core morphology for all the precursor fibers. Increase of lignin content in precursor fiber could reduce the portion of skin and cause obvious disorder of the meso- and molecular structure. By correlating structural variations with lignin blending, 30% lignin blending has been found as a potential balance point to obtain precursor fibers maintaining structural order together with high yield rate.