Lignin is one of the most abundant macromolecules on Earth. Lignins are obtained as by-products from the paper industry and used mostly as fuel. Their diverse composition has limited the development of high added-value applications: however, because of their abundance and sustainable origin, there is a growing interest in using lignins as a raw material and as a replacement for oil derivatives. In order to use lignins in bio-refineries, several processes must be studied and standardized. Lignin fractionation using solvents is a promising process. In this study, lignin from sugar cane bagasse (L1) was fractionated with solvents, and the fractions were characterized to evaluate structural aspects relevant for the production of fibers. L1 was extracted into four fractions with toluene (E1), ethanol (E2), methanol (E3), and dimethyl sulfoxide (DMSO, E4). Fractions E2, E3, and E4, showed only slightly different molar masses and molar mass distribution, but have relevant differences in their structural characteristics and processability. The ethanol extract (E2) provided lignins with a more flexible structure, and electro-spinning resulted in the production of nanofibers with diameters between 60 and 120 nm; the methanol fraction (E3) produced nanospheres with diameters between 90 and 350 nm; the DMSO fraction (E4) covered only a surface with electro-spray. These results show the possibility of developing high added-value applications using fractions of lignin from distinct biomasses or from their combination.