Deconvoluted IR-absorbance spectra of dextran, pullulan and gamma-irradiated pullulan were analyzed in order to find the most specific spectral peculiarities that allow one to obtain information about the structure and conformation of these macromolecules in solvents that exhibit different influences on the system of intra- and intermolecular interactions. The changes in intensity and width of the IR bands at about 1040, 1020 and, in the case of pullulan, also at 996 cm(-1), were related to changes in conformation and short-range interactions of the polysaccharides. Furthermore, certain bands within the 1200-900 cm(-1) region were considered as a characteristic for the type of glycosidic linkage. The results of the FTIR spectroscopy study allowed one to suggest a predominant cleavage of the alpha-(1-->4) linkages upon the radiation-chemical destruction of pullulan.