In this article, a facile, rapid, and efficient method was developed for the preparation of carboxymethyl hemicelluloses using microwave-induced organic reaction enhancement chemistry. The influences of the factors including reaction time, temperature, and the amount of sodium monochloroacetate and sodium hydroxide on the degree of substitution (DS) of the products were investigated. The rheological properties and the chemical structure of the resulting polymers were also studied. It was found that microwave irradiation could significantly promote the chemical reaction efficiency and accelerate the carboxymethylation of hemicelluloses with sodium monochloroacetate. Therefore, carboxymethyl hemicelluloses with higher DS of 1.02 could be obtained in much shorter time scales as compared to the conventional heating method. Results from rheological analysis indicated that carboxymethyl hemicellulose solutions exhibited shear-thinning behavior in the range of shear rates tested and showed lower viscosity and modulus in comparison with those of the native hemicelluloses due to lower molecular weight and the role of carboxymethyl groups in reducing the entanglements between hemicelluloses chains.