Poly(vinylidene difluoride) (PVDF) films were irradiated by means of heavy ions (in the electronic stopping-power range) and electrons. Both types of ionizing radiation induce in the polymer film ionizations and excitations, but swift heavy ions induce a huge density of excitations and ionizations along the ion path. Dose-range goes from 0.3 to 40 MGy. Irradiations were performed with Kr ions in the presence of helium, hydrogen, deuterium, and oxygen. Fourier transform infrared (FTIR) transmission measurements show differences in the nature of the created defects. Triple bonds are characteristic of the Kr ion irradiation. Double bonds, isolated and conjugated, exist for both kinds of radiation, but concentrations are higher with the Kr radiation. The presence of oxygen during irradiation produces oxidization defects. Typical bands of hydroxyls and carbonyls can be seen, respectively, in the 3800-3000 cm-1 zone and ca. 1850-1730 cm-1. The formation of conjugated double bonds is enhanced when the Kr irradiation is performed under an O2 atmosphere.