The polymer poly(vinylidene fluoride) (PVDF) was irradiated with X-rays produced by a nonmonochromatic (MgK alpha) source and the structural and electronic PVDF surface modifications were studied by X-ray photoelectron spectroscopy (XPS). Changes in the shape and intensity of the C-1s and F-1s lines show that a PVDF degradation consisting of the polymer defluorination takes place.