Understanding the dynamics of water in solid-state polymer electrolytes (e.g., Nation) is important for a variety of applications ranging from membrane-based water purification to hydrogen fuel cells. In this study, the dynamics of water in Nation was investigated at both low and high humidities with time-resolved Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectroscopy; a technique that provides a molecular fingerprint of both the diffusant and the polymer simultaneously in real time. At low humidities (0-22% RH), an extended initial time lag resulted in non-Fickian behavior, where dynamic infrared data provided evidence for a reaction between water and sulfonic acid. A diffusion reaction model was developed and predicted this anomalous behavior, where the time lag was a function of water content. At high humidities (0-100% R H), a slow approach to steady state resulted in non-Fickian behavior, where dynamic infrared data provided evidence of water-induced relaxation in the polymer backbone. A diffusion relaxation model was developed and regressed well to both the polymer relaxation and water diffusion data, where only one fitting parameter was used for each data set to determine both a relaxation time constant and diffusion coefficient, This approach differs significantly from previous work on non-Fickian) behavior in glassy polymers, which, consisted of regressing gravimetric data to models with a minimum of six fitting parameters. Not only do the diffusion coefficients from these two models compare well with Fickian diffusion coefficients from experiments with small water concentration gradients, but also the results in this study provide physical insight into the transport mechanisms of water and relaxation phenomena in solid-state polymer electrolytes.