Polyethylene oxide (PEO) polymers with well-defined chemical composition can induce and ion-polymer complex with well-defined molecular order. To study this, engineered PEO constructs consisting of ion-coordinating groups and low molecular weight polydispersities are used to quantify the influence of polymer charge and structure on ion conductivity and transference number. These effects can be further studied in terms of the dynamics of polymer nanostructure formation using ellipsometry, x-ray scattering and microrheology. Doing so will develop an understanding of fundamental phase behavior and polymer structure as it relates to organic electrolyte performance. This understanding can then be applied for rational electrolyte design, optimizing useful nanostructures and mean free paths for Lithium cation transference.