The state of water in new types of polymer-based proton conductors has been characterized by FTIR spectroscopy. The materials were produced by sulfonation of poly(vinyl fluoride) (PVF) films with chlorosulfonic acid after electron beam or proton irradiation or without any preirradiation. Spectra in the O-H and O-D stretching regions and in the H-O-H (D-O-D) bending region were analyzed in terms of frequency position and relative intensity of the various components. We found that the state of water in the sulfonated PVF membranes (PVF-SA) membranes differs significantly from that of the bulk water, and both hydrogen-bonded and non-hydrogen-bonded wafer molecules were detected. It is also found that the materials display the presence of a large number of proton complexes such as H3O+ or H5O2+. The study demonstrates furthermore that proton irradiation makes the material more hydrophilic than electron irradiation, which can be explained by the different nature of the irradiation effects.