In this paper chemical modification of a poly(vinylidene fluoride) surface by extreme ultraviolet (EUV) irradiation in a presence of ionized nitrogen was demonstrated for the first time. Nitrogen gas, injected into an interaction region, was ionized and excited by the EUV radiation from a laser-plasma source. The ionization degree and excited states of nitrogen were investigated using EUV spectrometry and the corresponding spectra are presented. Chemical modification of polymer after combined EUV and ionized nitrogen treatment was investigated using X-ray photoelectron spectroscopy. A significant contribution of nitrogen atoms in near-surface layer of the polymer after the treatment was demonstrated.