Providing sustainable supplies of purified water and energy is a critical global challenge for the future, and polymer membranes will play a key role in addressing these clear and pressing global needs for water and energy. Polymer membrane-based processes dominate the desalination market because they are more energy efficient than thermal desalination processes, and polymer membranes are crucial components in several rapidly developing power generation and energy storage applications that rely on membranes to control, selectively, rates of ion transport. Much remains unknown about the influence of polymer structure on basic intrinsic transport properties, and these relationships are important for designing next generation polymer membrane materials.Key to controlling ion transport in membranes for water purification and energy applications is engineering interactions between ions and the solvated polymer matrix. Microwave dielectric relaxation spectroscopy is a tool that enables study of hydrated polymer membranes because water molecule dipoles can be probed in the microwave frequency region. This technique can provide unique insight into hydrated polymer dielectric permittivity (or dielectric constant) properties, which are critical in emerging thermodynamic modeling of ion transport in hydrated polymers. This presentation discusses the use of microwave dielectric relaxation spectroscopy to uncover structure property relationships in hydrated polymers and, more broadly, presents an overview of research aimed at further understanding fundamental structure/property relationships that govern small molecule transport in polymeric materials considered for desalination and electric potential field-driven membrane applications that can help address global needs for clean water and energy.