Four populations of switchgrass (Alamo, GA993, GA992, Kanlow), Panicum virgatum L., were studied for the difference of their chemical constituents. The extractives, Klason lignin, and carbohydrates compositions of the stem portion of these switchgrass populations were determined by gas chromatography mass spectroscopy (GC-MS) and high performance anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD) respectively. Ball milled grass lignin (BMGL) was isolated and analyzed by NMR spectroscopy. The results demonstrated that the chemical compositions of four switchgrass populations were similar with the exception of the lignin content and chemical composition of extractives. The results of quantitative C-13 NMR spectroscopy indicated that switchgrass lignin consisted of p-hydroxylphenyl, guaiacyl, and syringyl units in an average ratio of 26:42:32 and incorporated with p-coumaric acid and ferulic acid at a level of approximately 0.20 per aromatic ring. The lignin structure of four switchgrass cultivars was comparable. (C) 2009 Elsevier Ltd. All rights reserved.