Polymer electrolyte lithium batteries represent the future of safe, high-energy battery systems. Although great strides have been made in the development of new polymer electrolytes and in understanding how these systems function, progress has been evolutionary in its scope. Further advancement of ambient temperature polymer electrolyte batteries will require new approaches that break with tradition. This report deals with new types of liquid polymers that have not been extensively described in the literature. The work presented in this report represents the beginning of the development of new solid polymer electrolytes. These heteroatomic materials combine the better features of several elements to solubilize and transport select lithium salts more efficiently than traditional ethylene oxide-type polymers. Ambient temperature ionic conductivities of >1×10−3 S/cm are common with this class of polymer electrolytes. An overview and rationale of the approach together with reported materials properties are reported.