Electron spin resonance (ESR) was used to monitor the local environment of 2,2,6,6-tetramethyl-4-piperidone N-oxide (Tempone) spin probe in water and methanol mixtures in solution and in Li+ ion exchanged Nafion 117 membranes. Solution spectra were analyzed using the standard fast-motion line width parameters, while membrane spectra were fitted using the microscopic order macroscopic disorder (MOMD) slow-motional line shape program of Freed and co-workers. The N-14 hyperfine splitting, a(N), which reflects the local polarity of the nitroxide probe, decreases with increasing methanol concentration, consistent with the decrease in solvent polarity. The polarity depended only weakly on composition in the Nation membrane, but was noticeably more temperature-dependent. The microviscosity of the membrane aqueous phase as reflected by the rotational correlation time (tau(c)) of the probe, was nearly 2 orders of magnitude longer in the membrane than in solution and varied by an order of magnitude over the composition range studied. The probe exhibits significant local ordering in the aqueous phase of Nation membranes that is diminished with increasing methanol concentration.