Fluoroethylene-carbonate is often referred to as a film-forming electrolyte additive for Li-ion batteries, resulting in high quality Solid–Electrolyte-Interphase on negative electrode, however, the underlying mechanism, even if thought to be known, has been only clarified due to our targeted experimental design, combining systematic electrochemical, chemical and microscopy characterization techniques. We have shown that first the formation of inorganic LiF-rich particles appear and only later the carbonate-rich film is actually formed.