Organosolv lignins were extracted from corn stover, wheat, rice straw, reed straw, and sugarcane bagasse using a mixture of acetic and formic acids, at relatively low temperature and atmospheric pressure. Lignin content, residual carbohydrates, ash levels, proteins, and molecular weights were determined in each extracted lignin. The lignin content of all samples was relatively high, confirming the performance of the pretreatment process. The low molecular weights were in a narrow range, in accordance with the organosolv lignin molar masses. However, some differences between studied lignins were highlighted, in particular in rice straw lignin, which contained the highest silica, calcium, and nitrogen contents. Nuclear magnetic resonance spectroscopies (31P and semi-quantitative Heteronuclear Single Quantum Correlation) underlined the structural similarities and differences between these organosolv lignins. Corn stover and sugarcane bagasse lignins were rich in non-methoxylated (H-Unit) or mono-methoxylated (G-Unit) phenolic units, making them the best promising candidates for production of phenolic resins. Wheat straw lignin was richer in aliphatic OH than in phenolic OH. This is an advantage for use as polyol substitute in polyurethane synthesis. Reed straw lignin was less specific, with a balanced content of OH groups. However, it contained a high concentration of β-O-4 linkages, which is favorable for depolymerization.