In the course of γ-irradiation at 77 K, polyvinyl alcohol accumulates alkyl radicals (formed upon hydrogen atom abstraction) and radical anions (resulting from electron addition to the acetate group remaining after the saponification of polyvinyl acetate in the course of polyvinyl alcohol production on its basis). Upon the radiolysis of polyvinyl alcohol at 300–341 K, polyenyl radicals with a singlet spectrum were detected in the EPR spectrum in addition to the triplet of alkyl radicals.