The interest in application of high-energy ionizing radiation for stenlization of pharmaceutical products and foodstuffs has led a number of workers to investigate the radiation sensitivity of vitamins. Aside from its use as a vitamin, ascorbic acid (AA) or some derivatives are employed as antioxidants in foodstuffs. The effects of ionizing radiation on AA in simple solutions and in mixture of naturally occurring compounds have been extensively reported in the literature. However, the effects of ionizing radiation on solid AA were reported in few works which described rather dosimetric features of AA No reports, except one, are available describing the characteristic features of the radiolytic intermediates produced after irradiation of polycrystalline AA. Irradiation studies performed on single crystal of AA has led us to reinvestigate our previous work on the radiolytic intermediates produced in irradiated polycrystalline AA. Three radical species, rather than two, having different characteristics were decided contributing to the formation of experimental electron spin resonance (ESR) spectrum of gamma-irradiated polycrystalline AA. Spectral parameters of these species were calculated after exhaustive spectrum simulation calculations based on data derived from experimental microwave saturation and dose-response studies.