The sorption kinetic and equilibrium data obtained at different water activities allowed us to determine the water sorption isotherms and mean diffusion coefficient in the Nation ® membrane. The water sorption isotherm is reminiscent of systems in which there is water clustering at high water activities, with a marked Langmuir sorption at low water activity for the acid form of the membrane. The variation of the diffusion coefficient with the water activity showed a maximum value whose coordinates depend on the counter-cation nature. The smaller the counter-cation, i.e. the larger the counter-cation hydration energy, the higher the diffusion coefficient and the lower the water activity at the maximum point.