Abstract As the core component of all‐solid‐state batteries, current solid‐state electrolytes fail to simultaneously meet multiple demands, such as their own high performance, the chemical, electrochemical and mechanical compatibility of electrode interface. A fresh perspective is rather desired to guide the development of novel solid electrolytes with comprehensive performance. Herein, this work proposes a novel strategy to synthesize solid electrolytes extracted from cathode‐electrolyte interphase (CEI), which is inspired by peach trees secreting peach gum to prevent further damage. A proof‐of‐concept, using LiBH 4 ‐Se and LiBH 4 ‐S as prototypes, confirms that as‐synthesized electrolytes inherited and improved up the advantages of LiBH 4 with unexpected compatibility toward multiple cathodes. It is believed that the family of new electrolytes will be continuously expanded under the guidance of this CEI‐derived concept.
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