Ammonia is used extensively as a fertilizer in agriculture and in the chemical industry. It also has the potential to store carbon-neutral fuel (hydrogen) in the future. To help meet the future demand for ammonia, the electrochemical nitrogen reduction reaction (NRR) has received much attention. It would serve as a decentralized method of synthesizing ammonia at low temperature and pressure. [1] To this day, the most promising NRR results have been shown via the lithium-mediated approach, in which lithium metal is electroplated in an organic electrolyte containing a lithium salt, saturated nitrogen gas, and a proton shuttle. The saturated nitrogen in the electrolyte reacts with electrodeposited lithium and protons are subsequently delivered by the shuttle. The local availabilities of protons and nitrogen are crucial for achieving a high selectivity towards ammonia rather than hydrogen evolution. The selectivity is heavily affected by the solid electrolyte interphase (SEI) which is formed between the electrodeposited lithium and bulk electrolyte. [2,3,4,5] This study investigates the role of ethanol as the proton shuttle in the lithium-mediated nitrogen reduction reaction (Li-NRR). In situ mass spectrometry and electrochemical quartz crystal microbalance are used to elucidate the importance of ethanol. Furthermore, particularly designed chronopotentiometry experiments are designed to provide additional information, allowing for a detailed discussion of ethanol’s multifaceted role in the Li-NRR. It is shown that ethanol is crucial for the formation of the SEI, but not necessary for the actual synthesis of ammonia. The SEI formation in the Li-NRR system is critically influenced by ethanol at the onset of lithium plating. Ethanol is not necessary to shuttle protons from the anode to the cathode. Furthermore, it is shown that lithium is an active species in the Li-NRR system even without electrochemistry. Finally, it is revealed that ethanol plays an important role in the context of anodic electrode potentials and electrolyte stability. References MacFarlane, D. R. et al. Adv. Mater. 32, 1904804 (2020) Du, H-L et al. Nature 609, 722 (2022) Lazaouski, N. et al. ACS Catal. 12, 5197-5208 (2022) Andersen, S. Z. et al. Energy Environ. Sci. 13, 4291-4300 (2020) Andersen, S. Z. et al. Nature 570, 504 (2019)