Food preservation is one of the practical applications of radiation processing of materials. Starch is an abundant and cheap nutritious biopolymer and also is the material for appropriate food systems and for technical industries. Starch granules are partially crystalline structures composed mainly of two types of starch: amylose, an essentially linear polymer, and amylopectin, with 3-44% of branch points. Electron spin resonance (ESR) spectroscopy is a very powerful and sensitive method for the characterization of the electronic structures of materials with unpaired electrons. The aim of the present work was to monitor the disappearance of the shortlife and long-life free radicals formed during ??-irradiation of 3 different starches. Corn, potato and fermented cassava starches were irradiated in a 60Co source Gammacell 220 with 20 kGy, dose rate around 1 kGy h-1. EPR spectra were obtained at room temperature using a Bruker EMX plus model, X band equipment. The main type of ESR signal from irradiated starch is a singlet with a g-value of about 2.0. The fading of ESR signals was followed for 350 hours, and presents differences among the different starch type reflecting differences in molecular arrangements of starch crystalline and amorphous fractions, although ESR spectra seemed to be common for all starches.