Six hemicellulosic fractions were extracted successively from dewaxed wheat straw with sodium hydroxide at increasing strength from 0.25 to 2.00M, and the chemical composition are reported. The structure of the hemicellulosic fraction 2 was investigated using acid hydrolysis, methylation analysis and 13C-NMR experiments. The hemicelluloses were confirmed to be a (1→4)-linked β-D-xylan with D-glucopyranosyluronic acid (or 4-O-methyl-α-D-glucopyranosyluronic acid) group attached at position 2, and L-arabinofuranosyl and D-xylopyranosyl groups attached at position 3. For every 26 D-xylopyranosyl residues in the main chain, there was one uronic acid unit. For 13 such D-xylopyranosyl residues, there was one L-arabinofuranosyl group, and for 18 such D-xylopyranosyl residues, there was one D-xylopyranosyl group.