The studies on the radical oxidation and depolymerization of polysaccharides in biological tissues and food stuffs published in recent years are reviewed and summarized. The radical reactions of polysaccharides taken up in here are initiated by the ionizing radiation and the action of active oxygen species, i.e. superoxide anion radical, hydrogen peroxide and hydroxyl radical. (1) Starch radicals formed in radiolysis transferred to soluble dextrins and low molecular carbonyl compounds through their radical rearrangements. These products decreased markedly with increase of moisture content in starch. Radiolysis mechanism has been proposed as shown in Schemes. (2) The active oxygen radicals from some oxidase systems and ascorbic acid-metal ion system depolymerize many kinds of polysaccharides, i.e. hyaluronate, pectin, starch and etc. These depolymerizations were inhibited by the addition of SOD, catalase and some hydroxyl radical scavengers, and a main principle in radical species has been estimated as hydroxyl radical. These interactions seemed to be associated with the biodeterioration in biological bodies and food stuffs.