To develop new ionomers and optimize existing ones, there is a need to understand their structure/function relationships experimentally. In this letter, synchrotron X-ray microtomography is used to examine water distributions within Nafion, the most commonly used ionomer. Simultaneous high spatial (1 μm) and temporal (10 min) resolutions, previously unattained by other techniques, clearly show the nonlinear water profile across the membrane thickness, with a continuous transition from dynamic to steady-state transport coefficients with the requisite water-content dependence. The data also demonstrate the importance of the interfacial condition in controlling the water profile and help to answer some long-standing debates in the literature.