The self-diffusion coefficient of water, D, in proton exchange membranes (PEMs) based on crosslinked-polytetrafluoroethylene (cPTFE) films was measured by a radioactivated-tracer permeation technique using tritium labeled water (HTO). The D value was found to increase with the water volume fraction of the PEM, φ, probably because the water-filled regions were more effectively interconnected with each other at high φ, allowing water permeation to be faster through a PEM. Interestingly, the grafted PEMs showed the lower D compared to that of Nafion in spite of their high φ. This would be caused by tortuous structures of transport pathways and a strong coulombic interaction between water and the negatively-charged sulfonate (SO3−) groups. Heavy-oxygen water (H218O) was also used in the similar permeation experiment to obtain the D. Since the HTO diffusion actually occurred not only by translational motion of water but also by intermolecular hydrogen-atom hopping, comparing the D of HTO with that of H218O was likely to give the information about the state of water in the PEMs.