Seven kinds of poly(vinylidene fluoride) (PVDF) specimens with different crystallinity are irradiated with electron beam. The radiation effects on the amorphous and crystal zones and the relationship between the structures of the materials and the radiation effects are discussed. Differential scanning calorimeter (DSC), electron spin resonance (ESR) and X ray diffraction are used to study the radiation damage of PVDF crystal. The zero entropy production phase transition temperature, the irradiation damage yield of crystal zone and the destiny of the residual free radical of macromolecules produced by irradiation are all discussed. It is shown that appreciable structural defects and distortions start from both of the deformed points of regularly folded crystalline stems and the irregular loop zone of the crystalline surface layers. Seven kinds of poly (vinylidene fluoride) (PVDF) specimens with different crystallinity are irradiated with electron beam. The radiation effects on the amorphous and crystal zones and the relationship between the structures of the materials and the radiation effects are discussed. Differential scanning calorimeter ( DSC), electron spin resonance (ESR) and X ray diffraction are used to study the radiation damage of PVDF crystal. The zero entropy production phase transition temperature, the irradiation damage yield of crystal zone and the destiny of the residual free radical of macromolecules produced It is shown that appreciable structural defects and distortions start from both of the deformed points of regularly repeating crystalline stems and the irregular loop zone of the crystalline surface layers.