Food irradiation is a "cold" process for preserving food and has been established as a safe and effective method of food processing and preservation after more than five decades of research and development. The small temperature increase, absence of residue and effectiveness of treatment of pre-packed food are the main advantages. In food industry, ascorbic acid and its derivatives are frequently used as antioxidant agents. However, irradiation is expected to produces changes in the molecules of food components and of course in the molecules of the agents added as preservation agents such as ascorbic acid. These changes in the molecular structures could cause decreases in the antioxidant actions of these agents. Therefore, the radiation resistance of these agents must be known to determine the amount of radiation dose to be delivered. Electron spin resonance (ESR) is one of the leading methods for identification of intermediates produced after irradiation. ESR spectrum of irradiated solid powder of ascorbic acid is fairly complex and determinations of involved radical species are difficult. In the present work, single crystals of ascorbic acid irradiated by gamma radiation are used to determine molecular structures of radiation induced radicalic species and four radicalic species related in pair with P2(1) crystal symmetry are found to be responsible from experimental ESR spectrum of gamma irradiated single crystal of ascorbic acid.