Abstract Carbonate‐based electrolytes are incompatible with lithium (Li) metal anode because the generated solid electrolyte interphase (SEI) undergoes repeated breakage‐repair, resulting in the accumulation of inactive Li including Li + compounds and electrically isolated dead Li 0 in the SEI. Therefore, exploiting a suitable strategy to construct a stable SEI while efficiently rejuvenating the inactive Li capacity is urgent and more thoughtful than just building a stereotyped SEI layer. Herein, an innovative strategy is proposed of high‐concentration additive (HCA) of LiNO 3 inspired by (localized) high‐concentration electrolyte and inactive Li restoration methodology via triiodide/iodide (I 3 − /I − ) redox couple to improve the compatibility of carbonate‐based electrolytes. The HCA of LiNO 3 can maintain the cation–anion aggregates solvation structures in the carbonate‐based bulk electrolyte and induce the in situ formation of superior‐ionic‐conductivity NO 3 − ‐derived SEI. Moreover, the reversible I 3 − /I − redox couple can further optimize the SEI and constantly rejuvenate the inactive Li including solvent/LiNO 3 ‐derived Li 2 O, a derivative has almost been acquiescent in LiNO 3 ‐additive electrolytes, and dead Li 0 into delithiated cathode. Consequently, epitaxy‐like planar Li deposition, better reversibility, and higher capacity retention can be realized and are systematically verified by Li||Cu half cells, full cells with excess/limited Li (N/P ratio = 1.5) and anode‐free lithium metal batteries.