The effect of vinylene carbonate (VC) as electrolyte additive on the formation mechanisms of passivation films covering both electrodes in lithium-ion batteries was investigated by X-ray photoelectron spectroscopy (XPS). <mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">Li</mml:mi><mml:mi mathvariant="normal">Co</mml:mi><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mrow><mml:mn>2</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math>LiCoO2 /graphite coin cells using a <mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">Li</mml:mi><mml:mi mathvariant="normal">P</mml:mi><mml:msub><mml:mi mathvariant="normal">F</mml:mi><mml:mrow><mml:mn>6</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math>LiPF6 /ethylene carbonate:diethyl carbonate:dimethyl carbonate liquid electrolyte with or without VC were charged at 20 and <mml:math display="inline"><mml:mrow><mml:mn>60</mml:mn><mml:mo>°</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math>60°C . The identification of VC-derived products formed at the surface of the electrodes was carried out by a dual experimental/theoretical approach. From a classical XPS core peak analysis completed by a detailed interpretation and simulation of valence spectra supported by ab initio calculations, and through direct synthesis of the VC polymer, we could evidence the formation of the radical poly(VC) at the electrode/electrolyte interfaces. We showed that the radical polymerization is the main reaction mechanism of VC contributing to the formation of the passivation layers at the surface of both electrodes.