Ion-bombarded polystyrene with a 0.5-keV Ar+ beam has been investigated by means of photoelectron spectroscopy performed with synchrotron radiation. After a dose of 10(15) ions/cm2 the evolution of the valence band of the bombarded sample towards an amorphous carbonlike configuration is reported. From the analysis of valence-band spectra we estimated the out-diffusion of hydrogen and showed that its electronic states remain well identified and stable until the hydrogen presence is about 35% with respect to the pristine sample. Finally, comparison with mass spectroscopy measurements on deuterated polystyrene has been performed to determine hydrogen evolution during the ion irradiation.