Wheat straw hemicelluloses were converted to novel bifunctional hemicellulosic derivatives by etherification using acrylamide as reactant and sodium hydroxide as catalyst. The degree of substitution can be monitored by altering the molar ratio of acrylamide to xylose unit in hemicelluloses in the range of 1.0-10.0 and the molar ratio of sodium hydroxide to xylose unit in hemicelluloses in the range of 0.5-1.6, without changing the structure of the hemicelluloses. Comparison of the reaction in different media is discussed in detail. The optimized product with a high DS value of 0.58 was obtained by varying the condition parameters. Novel hemicellulosic derivatives containing carbamoylethyl and carboxyethyl groups could be confirmed by FT-IR, (1)H NMR, and (13)C NMR spectroscopies. The behavior of hemicellulosic derivatives was monitored by means of thermogravimetry (TG) and differential thermal analysis (TGA). It was found that the product with a high DS had a lower thermal stability than the native hemicelluloses.