The samples of poly(vinylidene fluoride) (PVDF) filmwas exposed to long termAlKá radiation, electrons and ion bombardment with the aimof surface carbonization. An influence of secondary electrons on the electron emission spectra of PVDF film and its carbonized derivatives has been studied. Original routines of the CKVV and C1s spectra shape parameterization for PVDF and its dehydrofluorinated derivatives have been developed and carefully described. Analysis of C1s and C KVV lineshape has revealed obviously different electronic structure of carbonized layers derived fromPVDF via two kinds of radiative treatment. In case of Ar+ bombardment the sp2- bonds predominate. The Al Ká irradiation leads to some other form(s) of carbon, but additional ion bombardment transforms them into species with predominating sp2-bonding. The most puzzling result of this study is that both photons and ions produce the same depth gradient of fluorine in the layers of carbonized surface accessible for XPS analysis.