It is well known that the proton-exchange membrane is perhaps the most critical component of a polymer-electrolyte fuel cell. Typical membranes, such as Nafion® , require hydration to conduct efficiently and are instrumental in cell water management. Recently, evidence has been shown that these membranes might have different interfacial morphology and transport properties than in bulk. In this paper, experimental data combined with theoretical simulations that explore the existence and impact of interfacial resistance on water transport for Nafion® membranes will be presented. A mass-transfer coefficient for the interfacial resistance is calculated from experimental data using different permeation cells. This coefficient is shown to depend exponentially on relative humidity or water activity. The interfacial resistance does not seem to exist for liquid/membrane or membrane/membrane interfaces. The effect of the interfacial resistance is to flatten the water content profiles within the membrane during operation. Under typical operating conditions, the resistance is on par with the water transport resistance of the bulk membrane. Thus, the interfacial resistance can be dominant especially in thin, dry membranes and can affect overall fuel cell performance.