Quantitative electron paramagnetic resonance (EPR) spectroscopy was used for the determination of a number and properties of short-living radicals generated thermally in maize starch with various amounts of amylose. The EPR spectra of radical adducts with N-tert-butyl-α-phenylnitrone (PBN) spin trap reveal the presence of three types of radicals of mobility related with their localization in the zones of various degree of crystallinity. Hylon VII, which represents a matrix with a high content of amylose, offers better conditions for free rotation of radical species, whereas waxy maize, containing almost exclusively amylopectin, exhibits more restricted dynamics.