This paper covers the synthesis and use of a related family of cyclic phosphazene solvents containing terminal unsaturations that are being considered as electrolyte additives in lithium-ion cells. A brief synopsis on the synthesis and purification of these compounds is given. Data will be presented that covers physical and chemical properties of the phosphazenes as well as the properties when blended at various levels with representative organic carbonate baseline solvents. Electrochemical cycling data will be presented using commercially available electrode couples as well as studies focusing on cell performance at early lifetime as well as after repeated cycles. Conclusions regarding the effect of the unsaturated phosphazene compounds and their interaction with various alkyl carbonates, and their effect on cell performance will be presented.