There is growing demand for a more efficient use of polymers that originate from renewable feedstocks due to the depleting supply of fossil fuels, based on economic and environmental reasons. As a result, lignin has attracted renewed interest as a resource for various bioproducts. Lignin is a natural biopolymer with a high carbon content and is composed of aromatic moieties, with a high level of polar functionalities. This makes it a unique precursor for certain high-value applications, such as in biofuels, bioplastics, composite materials, carbon fibers and activated carbons and as a source of phenolic monomers and fine chemicals. Industrial lignins are formed as byproducts of pulping processes (such as kraft, sulfite or alkaline pulping) or result from the biorefining process, where carbohydrates are used for sugar production. Lignin’s intrinsic structure is significantly modified during the processing of lignocellulose, resulting in the formation of more diverse, condensed and less reactive raw materials. Since molecular mass and polydispersity are the most important parameters affecting the chemical reactivity and thermal properties of lignin, additional process steps to improve the quality of crude technical lignins, including kraft lignin, are needed. Solvent extraction is a potentially useful technique for further improving the polydispersity of technical lignins. This work summarizes the impact of solvent fractionation on the chemical structure, antioxidant activity, heating value, and thermal and sorption properties of industrial hardwood and softwood kraft lignins. The purpose was to understand the correlation between certain structural features in the lignin fractions and their properties to select the appropriate solvent combinations for specific applications of lignin raw materials. Four common industrial solvents, namely, ethyl acetate, ethanol, methanol and acetone, in various combinations were used to separate both spruce and eucalyptus kraft lignins into fractions with lower polydispersities. Gel-permeation chromatography analysis was used to evaluate the efficiency of the chosen solvent combination for lignin fractionation. The composition and structure of the lignin material were characterized by elemental analysis, analytical pyrolysis (Py-GC/MS/FID) and 31P NMR spectroscopy. The thermal properties of the lignin samples were studied by thermogravimetric analysis. Proximate analysis data (ash, volatile components, organic matter and fixed carbon) were obtained through the direct measurement of weight changes during the analysis, while the high heating values (in MJ/kg) were calculated according to equations suggested in the literature. The sorption properties of fractionated kraft lignins were studied with respect to methylene blue dye. Additionally, lignin fractions with different molecular weights (and therefore various chemical structures) that were isolated from both softwood and hardwood kraft lignins were incorporated into a tunicate cellulose nanofiber (CNF)-starch mixture to prepare 100% bio-based composite films. The aim was to investigate the correlation between lignin diversity and film performance. The transmittance, density and thermal properties of the films were investigated, as were their mechanical properties, including the tensile stress and Young’s modulus. This part of the study addressed the importance of lignin diversity on composite film performance, which could be helpful for tailoring lignin applications in bio-based composite materials based on the material’s specific requirements.