AbstractUtilization of lithium (Li) metal anodes in all‐solid‐state batteries employing sulfide solid electrolytes is hindered by diffusion‐related dendrite growth at high rates of charge. Engineering ex‐situ Li‐intermetallic interlayers derived from a facile solution‐based conversion‐alloy reaction is attractive for bypassing the Li0 self‐diffusion restriction. However, no correlation is established between the properties of conversion‐reaction‐induced (CRI) interlayers and the deposition behavior of Li0 in all‐solid‐state lithium‐metal batteries (ASSLBs). Herein, using a control set of electrochemical characterization experiments with LixAgy as the interlayer in different battery chemistries, this work identifies that dendritic tolerance in ASSLBs is susceptible to the surface roughness and electronic conductivity of the CRI‐alloy interlayer. This work thereby tailors the CRI‐alloy interlayer from the typical mosaic structure to a hierarchical gradient structure by adjusting the pit corrosion kinetics from the (de)solvation mechanism to an adsorption model, yielding a smooth organic‐rich outer layer and a composition‐regulated inorganic‐rich inner layer composed mainly of lithiophilic LixAgy and electron‐insulating LiF. Ultimately, desirable roughness, conductivity, and diffusivity are integrated simultaneously into the tailored CRI‐alloy interlayer, resulting in dendrite‐free and dense Li deposition beneath the interlayer capable of improving battery cycling stability. This work provides a rational protocol for the CRI‐alloy interlayer specialized for ASSLBs.