Electrolyte additives have been widely used to address critical issues in current metal (ion) battery technologies. While their functions as solid electrolyte interface forming agents are reasonably well‐understood, their interactions in the liquid electrolyte environment remain rather elusive. This lack of knowledge represents a significant bottleneck that hinders the development of improved electrolyte systems. Here, the key role of additives in promoting cation (e.g., Li+) desolvation is unraveled. In particular, nitrate anions (NO3−) are found to incorporate into the solvation shells, change the local environment of cations (e.g., Li+) as well as their coordination in the electrolytes. The combination of these effects leads to effective Li+ desolvation and enhanced battery performance. Remarkably, the inexpensive NaNO3 can successfully substitute the widely used LiNO3 offering superior long‐term stability of Li+ (de‐)intercalation at the graphite anode and suppressed polysulfide shuttle effect at the sulfur cathode, while enhancing the performance of lithium–sulfur full batteries (initial capacity of 1153 mAh g−1 at 0.25C) with Coulombic efficiency of ≈100% over 300 cycles. This work provides important new insights into the unexplored effects of additives and paves the way to developing improved electrolytes for electrochemical energy storage applications. The key role of additives in promoting Li+ desolvation in battery electrolytes is unraveled. The nitrate (NO3−) anions are found to incorporate into the solvation shells, change the local environment of Li+ ions and their coordination in the electrolyte, resulting in more efficient Li+ desolvation and significantly enhanced battery performance.