The chemical changes that occur on the surface of poly(vinyliden fluoride) (PVDF) irradiated with 1.3 Mev electrons at doses up to 30 MGy, were studied by X-ray photoelectron spectroscopy (XPS) and by infrared spectroscopy (FTIR) in the horizontal attenuated total reflectance mode (HATR) and in the transmission mode. The wetability of the surface before and after irradiation was measured by dynamic contact angle measurements. The C1s structure in XPS reveals that as a result of irradiation, the -CF2- related peak practically disappears. The remaining C1s peak is mainly associated with C=C bonds in the heavily cross-linked carbon structure produced as a result of irradiation. FTIR spectra are consistent with the XPS observations. The irradiated films showed improvement in the oxidation and wetability of the surface.