The role of vinylene carbonate (VC) as a thermal additive to electrolytes in lithium ion batteries is studied in two aspects: the protection of liquid electrolyte species and the thermal stability of the solid electrolyte interphase (SEI) formed from VC on graphite electrodes at elevated temperatures. The nuclear magnetic resonance (NMR) spectra indicate that VC can not protect LiPF6 salt from thermal decomposition. However, the function of VC on SEI can be observed via impedance and electron spectroscopy for chemical analysis (ESCA). These results clearly show VC-induced SEI comprises polymeric species and is sufficiently stable to resist thermal damage. It has been confirmed that VC can suppress the formation of resistive LiF, and thus reduce the interfacial resistance.