Poly(vinylidene fluoride) films were implanted with high‐energy (up to 6 MeV) He, C, O, and Ni ions and characterized using DSC, FTIR, and solubility measurements. None of the ions were energetic enough to penetrate the polymer film completely. The effects of ion energy, fluence, and ion type were studied individually. The implantation process lowered the crystallinity, induced crosslinking, and produced carbonyl groups on the polymer. The ion energy (in the range 0.4–4.5 MeV for He ions) had the most drastic effect, the radiation damage was found to increase with decreasing energy. The sample implanted with 0.4 MeV He ions lost 81% of its initial crystallinity and was only 24% soluble, even though the incident ions have a range of only 2.7 μm in this case. The other samples retained most of their initial crystallinity but still were substantially cross‐linked. The results can be qualitatively explained by assuming that hydrogen free radicals, produced during implantation, can diffuse throughout the sample and react, resulting in crystallinity and solubility losses beyond the ion deceleration region.