Current and future demands for increasing the energy density of batteries without sacrificing safety has led to intensive worldwide research on all solid state Li-based batteries. Given the physical limitations on inorganic ceramic or glassy solid electrolytes, development of polymer electrolytes continues to be a high priority. This brief review covers several recent alternative approaches to polymer electrolytes based solely on poly(ethylene oxide) (PEO) and the use of nuclear magnetic resonance (NMR) to elucidate structure and ion transport properties in these materials.