Manifestation of stretching vibrations of glycosidic linkage in the infrared spectra of polysaccharides (native, microcrystalline, mercerized celluloses, amylose, starches) has been studied using the regularized method of deconvolution. It has been shown that the glycosidic linkage formation in the polysaccharides is characterized by the appearance of new absorption bands in the 1175–1140cm −1 range as compared to their corresponding monomers. In the 1000−920cm −1 region differences between the infrared spectra of polysaccharides due to the changes in the glycosidic linkage configuration have been found.