Atomistic molecular dynamics simulations are reported over a wide range of water contents and temperatures to obtain a better understanding of the structural and transport aspects of water sorption in Nafion, a perfluorosulfonic acid membrane, under equilibrium conditions. For the short Nafion chains studied, good agreement is found between the water sorption isotherms from simulations and experiments at intermediate hydration (2 ≲ λ ≲ 7, where λ is the number of water molecules per sulfonate group), suggesting that, in that range, the isotherm is insensitive to effects of polymer chain relaxation. If polymer chain relaxation were important for water sorption at these conditions, then the water uptake of experimental membranes, which contain very long chains, might be far from equilibrium, making it difficult to obtain agreement with equilibrated, short-chain simulations. At λ ≲ 7, strong water-sulfonate interactions, rather than chain relaxation, may control water sorption, despite the fact that chain relaxation time increases dramatically with decreasing hydration. Evidence for strong water-sulfonate interactions is found in the observation that sulfonate groups share water molecules in their first coordination shells at λ ≲ 7. Strong water-sulfonate interactions are also observed to influence transport properties like water diffusivity, and are as important for understanding these transport properties as larger-scale phenomena like morphology and percolation transitions. Finally, at low humidity (λ ≈ 1-2), rod-like hydrophilic clusters are observed, as well as a mechanism of water diffusion that differs qualitatively from that of water at high hydration (λ ≳ 7) and in the bulk, pure-component phase.