The syntheses of room‐temperature ionic liquids (RTILs) combining the naturally occurring amino acid l‐proline and ferrocene (Fc) building blocks are reported. After quaternization of ({[(2S)‐N‐methylpyrrolidine‐2‐yl]methyleneoxy}carbonyl)ferrocene (1) with alkyl iodides and anion exchange, the resulting diastereomeric (1S,2S)‐ and (1R,2S)‐[(ferrocenylcarbonyl)oxy]methylene‐N,N‐dialkylpyrrolidine‐1‐ium RTILs are redox‐active and air‐ and water‐stable. They are also thermally stable up to 263 °C. The electrochemical FeII/FeIII potential is shifted to +0.28 V versus Fc/Fc+. Before anion exchange, several iodide derivatives were obtained as crystalline products, and their crystal structures are reported. According to the NMR spectroscopic data cation–anion aggregates are present in the non‐coordinating solvent CDCl3. In contrast, in the polar solvent [D6]dimethyl sulfoxide ([D6]DMSO), the ion pairs are separated.