Lignin, a prominent constituent of woody biomass, is abundant in nature, cost-effective, and contains various functional groups, including hydroxyl groups. Owing to these characteristics, they have the potential to replace petroleum-based polyols in the polyurethane industry, offering a solution to environmental problems linked to resource depletion and CO2 emissions. However, the structural complexity and low reactivity of lignin present challenges for its direct application in polyurethane materials. In this study, Kraft lignin (KL), a representative technical lignin, was fractionated with ethanol, an eco-friendly solvent, and mixed with conventional polyols in varying proportions to produce polyurethane films. The results of ethanol fractionation showed that the polydispersity of ethanol-soluble lignin (ESL) decreased from 3.71 to 2.72 and the hydroxyl content of ESL increased from 4.20 mmol/g to 5.49 mmol/g. Consequently, the polyurethane prepared by adding ESL was superior to the KL-based film, exhibiting improved miscibility with petrochemical-based polyols and reactivity with isocyanate groups. Consequently, the films using ESL as the polyol exhibited reduced shrinkage and a more uniform structure. Optical microscope and scanning electron microscope observations confirmed that lignin aggregation was lower in polyurethane with ESL than in that with KL. When the hydrophobicity of the samples was measured using the water contact angle, the addition of ESL resulted in higher hydrophobicity. In addition, as the amount of ESL added increased, an increase of 7.4% in the residual char was observed, and a 4.04% increase in Tmax the thermal stability of the produced polyurethane was effectively improved.