Non-purified lignins resulting from ethanol-based organosolv fractionation of wheat straw were characterized for the presence of impurities (carbohydrates and ash), functional groups (hydroxyl, carboxyl and methoxyl), phenyl-propanoid structural moieties, molar mass distribution and thermal behavior. In accordance with its herbaceous nature, the syringyl/guaiacyl-ratio of the wheat straw lignins was substantially lower than of Alcell lignin. In addition, the content of p-hydroxyphenyl and carboxyl groups is substantially higher for the wheat straw lignins. The non-purified organosolv lignins had a high purity with 0.4–5.2% carbohydrate impurities, both originating from lignin to carbohydrate complexes and residual organosolv liquor. The use of H2SO4 in the organosolv process improved the lignin yield, but at low acid doses increased the carbohydrate impurities. For applications where a low amount of carbohydrates is important, lignin from a high-temperature autocatalytic organosolv process was found to be preferred. The highest content of total hydroxyl groups was determined when lignins were produced using 30 mM H2SO4 as catalyst or 50% w/w aqueous ethanol as solvent for the organosolv process. Aliphatic hydroxyl groups, the most predominant type of hydroxyl groups present originating for a substantial part from residual carbohydrates, were found to decrease with reaction time and ethanol proportion of the organosolv solvent. The correlations between organosolv process conditions and lignin characteristics determined can facilitate the use of organosolv lignins in value-added applications such as in polymers and resins and as a feedstock for bio-based aromatics.