Thermomechanical analysis of poly (vinylidene fluoride)(PVDF) film shows that, unlike the completely amorphous structure of the native polymer, after irradiation with X-rays, the weight fraction of the crystalline modification in the polymer is 0.5. The initial PVDF film had a linear thermal expansion coefficient of α 1= 11.33 х10 5 K− 1 and a glass transition temperature of T g= 256 K. An efficient conversion of the amorphous structures of the polymer pseudo-network into crystalline networks occurs under X-ray irradiation. The irradiated polymer exhibits amorphous (T g= 239 K) and crystalline topological blocks (T m= 385 K). The presence of polyenyl and alkyl radicals is found in the electron paramagnetic resonance (EPR) spectra of the irradiated polymer. Lines with a splitting of 3.3 m T can be observed at the edges of the EPR spectra, consistent with radical centers like-CF 2-C• H-CF 2-. At high doses of radiolysis, polyenyl radicals are the main observed radicals. The macromolecular chains contain all three (α, β, γ) morphologies of the polymer. The Raman spectra show that X-ray irradiation can lead to carbonization and the formation of unsaturated bonds. Electronic structure calculations were used to aid in the analysis of the observed spectra.