Redox shuttle electrolyte additives have been suggested as a possible mean of internal overcharge protection of secondary lithium-ion batteries. TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) is one of these redox shuttles for overcharge protection of 3V class Li-ion cells. The electrochemical reversibility and the diffusion coefficient of this molecule has been evaluated by mean of cyclic voltammetry. The redox shuttle voltage was found to be 3.5V versus Li/Li+ and D =cm2 s−1. The electrochemical stability of TEMPO in different overcharging conditions has been evaluated by long-term cycling using Li/Li4Ti5O12 cells. Results show that the TEMPO redox system does not act as an ideal shuttle. When dissolved in the electrolyte at 0.5M, this additive is able to level off the cell potential at 3.5V for a long period at low overcharging current (C/200 to C/50). Nevertheless, it appears that the cell capacity fades drastically at the first cycles and with time. This phenomenon is probably related to the stability of the oxidized and reduced form of the TEMPO molecule.