Here, we report on the electrochemistry and transport of ions in mixtures of carbonates and an electroactive ionic liquid, in which lithium bis­(trifluoromethylsulfonyl)­imide (Li­[NTf2]) is dissolved. The electroactive ionic liquid was obtained by linking a ferrocene moiety to the [NTf2]−, resulting in a redox anion (ferrocenylsulfonyl­(trifluoromethylsulfonyl)­imide, [FcNTf]−) that can be used as a redox shuttle additive in Li-ion battery electrolytes. Electrochemical and transport properties of the [FcNTf]− electroactive anion and of Li+ are investigated by ionic conductivity, cyclic voltammetry, and self-diffusion PFGSE NMR measurements. The study of the transport properties demonstrates the formation of solvated species and ion aggregation which affects the electrochemical behavior of the [FcNTf]− anion. This study highlights that the fractional lithium ion and total ionic conductivity were significantly decreased with a high concentration of ionic liquid and lithium salt. Finally, the electroactive ionic liquid was applied in lithium-ion cells as a proof of concept of their use as redox shuttles.