Transport and absorption in metal cation exchanged and polyvinylpyrrolidone (PVP) modified Nafion (R) films were studied by various techniques. To understand the microscopic basis for permeation, time resolved small angle X-ray scattering (SAXS) was used to characterize the ionic domain morphology while films were exposed to vapors of water, dimethyl methylphosphonate (DMMP), or triethyl phosphate. Macroscopic weight uptake studies of DMMP vapor into PVP-Nafion (R) were also used to help explain the SAXS absorption studies and DMMP permeation properties. The SAXS results were correlated with macroscopic permeation rates of DAMP, Soman, and water through several different membranes. To provide additional basis for the SAXS derived morphologies, tapping-mode AFM was also used to image the 3-5 nm diameter ionic domains. A goal for protective suit applications is to find films with a balance of high moisture permeation rate for comfort, and low DMMP permeation. The best balance of properties in this context was found with PVP- and zirconyl-modified films. In another extreme, the permeation rates of both water and DMMP through cesium-modified Nafion (R) were low. SAXS studies were used to explain this where the ionic domains of cesium-modified Nafion (R) did not "expand" when exposed to DMMP or water vapor. (C) 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 284-298, 2009