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Abstract Recently, lithium‐mediated nitrogen reduction reaction (Li‐NRR) in nonaqueous electrolytes has proven to be an environmentally friendly and feasible route for ammonia electrosynthesis, revealing tremendous economic and social advantages over the industrial Haber‐Bosch process which consumes enormous fossil fuels and generates massive carbon dioxide emissions, and direct electrocatalytic nitrogen reduction reaction (NRR) which suffers from sluggish kinetics and poor faradaic efficiencies. However, reaction mechanisms of Li‐NRR and the role of solid electrolyte interface (SEI) layer in activating N₂remain unclear, impeding its further development. Here, using electronic structure theory, we discover a nitridation‐coupled reduction mechanism and a nitrogen cycling reduction mechanism on lithium and lithium nitride surfaces, respectively, which are major components of SEI in experimental characterization. Our work reveals divergent pathways in Li‐NRR from conventional direct electrocatalytic NRR, highlights the role of surface reconstruction in improving reactivity, and sheds light on further enhancing efficiency of ammonia electrosynthesis.