The current highly flammable configurations for rechargeable lithium batteries generate safety concerns. Although commercial fire retardant additives have been investigated, they tend to decrease the overall efficiency of the battery. We report here ionically conductive, non-halogenated lithium battery additives based on a methoxyethoxyethoxyphosphazene oligomer and the corresponding high polymer, which can increase the fire resistance of a battery while retaining a high energy efficiency. Conductivities in the range of 10−4 Scm−1 have been obtained for self-extinguishing, ion-conductive methoxyethoxyethoxyphosphazene oligomers. The addition of 25wt% high polymeric poly[bis(methoxyethoxyethoxy)phosphazene] to propylene carbonate electrolytes lowers the flammability by 90% while maintaining a good ionic conductivity of 2.5×10−3 Scm−1.