[en] The atomic and electronic structure of polymer films undergoes deep modifications during high energy (keV-MeV) ion irradiation, from molecular solid to amorphous material. At low energy density (10²²-10²⁴ eV/cm³) typical effects include chain scissions, crosslinks, molecular emission and double bonds formation. In hydrocarbon polymer (polystyrene, polyethylene) the main effect of irradiation is the formation of new bonds as detected by molecular weight distribution, solubility and optical measurements. Moreover the concentration of trigonal carbon (sp²) in the polymer changes with ion fluence (10¹¹-10¹⁴ ions/cm²) and stabilizes to a value of 20% independently on the initial chemical structure of the irradiated sample. Photoemission spectroscopy shows an evolution of valence band states from localized to extended states. At high energy density (10²⁴-10²⁶ eV/cm³) the irradiated polymer continues to evolve showing spectroscopic characteristics close to those of hydrogenated amorphous carbon. Trigonal carbon concentration changes with ion fluence (10¹⁴-10¹⁶ ions/cm²) reaching the steady state value of 60% and the hydrogen concentration decreases to 20%. Moreover the values of the optical gap (2.5-0.5 eV) suggest the presence of medium range order in the obtained hydrogenated amorphous carbon. These values are consistent with the formation of graphitic clusters, whose size goes from 5 A to 20 A by changing the ion fluence (or energy density). (orig.)