The electron paramagnetic resonance (EPR) spectra of poly (vinylidene fluoride) (PVDF) films were studied in order to identify type and intensity of trapped radicals after an electron treatment with 150 kGy in air at room temperature. The observed EPR spectra consist of superimposed spectra of eight different radicals. The individual spectra were simulated by first derivatives of normalized Gaussian functions including intensity, linewidth, g value, and hyperfine splitting constants of the unpaired electron with hydrogen or fluorine atoms in α or β positions. In addition, the number of trapped radicals was estimated using a standard sample of known spin concentrations. Although initially generated radicals tend to be converted to peroxy radicals in the presence of oxygen, the predominant radical is the CH-based mid-chain radical (–CF₂–C*H-CF₂-) with a relative intensity of 62.3%. This is attributed to CH-based radicals in the crystalline domains with low molecular mobility leading to an enhancement in its linewidth (ΔH_pp ⁓ 3.6 mT). A fraction of 20.7% of all radicals are peroxy radicals with anisotropic g values, g_∥ = 2.0210 and g_⊥ = 2.0095. The relative intensity of allyl, dienyl and polyenyl radicals amounts to 4.9%.