This study provides insights into structure-property relationships of Nafion membranes swollen with organic sorbates, revealing correlations between sorbate polarity, ionomer domain structure, and ionic conductivity. Swelling, nanostructure, and ionic conductivity of Nafion in the presence of short-chain alcohols and alkanes was studied by infrared spectroscopy, X-ray scattering, and voltammetry. Nafion equilibrated with alkanes exhibited negligible uptake and nanoswelling, while alcohols induced nanoscopic- to macroscopic- swelling ratios that increased with alcohol polarity. In mixed-sorbate environments including organics and water, alcohols preserved the overall ionomer domain structure but altered the matrix to enable higher sorbate uptake. Alkanes did not demonstrably alter the hydrated nanostructure or conductivity. Identifying the impacts of organic sorbates on structure-property relationships in ionomers such as Nafion is imperative as membrane-based electrochemical devices find applications in emerging areas ranging from organic fuel cells to the synthesis of fuels and chemicals.