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Sulfonamides are used as active ingredients in different drugs to treat infections caused by bacteria. Sulfatiazole (STZ) is one of the commonly used sulfonamides as antibacterial agent in drugs, which constitute potential candidates for radiosterilization. However, the crucial point in this respect is to monitor the amount and characteristic features of the radiolytic intermediates produced after irradiation. Electron spin resonance (ESR) spectroscopy is extensively used for this purpose due to its high sensitivity toward intermediates exhibiting radicalic nature. Thus, the aim of the present work is to investigate the spectroscopic and kinetic features of the species having unpaired electrons induced in gamma irradiated STZ at room and different temperatures in the dose range of 5–50 kGy using ESR spectroscopy. Spectra of irradiated STZ consisted of many resonance peaks in the studied dose and temperature ranges. Heights of the peaks measured with respect to the base line were used to monitor microwave, temperature, time-dependent features of the radical species contributing to the experimental ESR spectra. Four tentative species of different spectroscopic and structural features assigned as A, B, C and D were found well explaining the experimental ESR spectra of gamma irradiated STZ. Comparison between the principal IR bands of unirradiated and gamma irradiated samples showed no detectable changes and appearance of new bands.