Li-mediated nitrogen reduction reaction (Li-NRR) has emerged as a promising alternative to the traditional Haber–Bosch process for ammonia synthesis, offering the potential for sustainable and energy-efficient production under ambient conditions. Over the past 5 years, Li-NRR research has grown significantly, leading to rapid advancements in ammonia production rates and Faradaic efficiency. This review focuses on the recent advancements in Li-NRR, with a particular emphasis on strategies aimed at improving system stability. Various strategies to enhance the stability of Li-NRR systems are categorized and analyzed, including the optimization of proton carriers, the design of favorable solid-electrolyte interphases, and the regulation of anodic reactions to prevent electrolyte decomposition. The review also highlights the growing importance of materials selection and reaction conditions, such as electrolyte composition and electrode design, in achieving high Li-NRR system stability. Despite rapid progress, several current challenges are identified, and future directions for research to create more robust and sustainable Li-NRR systems are proposed. This work aims to provide insights into the critical factors that drive the performance and stability of Li-NRR and to inspire future efforts toward the development of efficient and scalable ammonia synthesis technologies.