Protection of lithium (Li) metal electrode is a core challenge for all‐solid‐state Li metal batteries (ASSLMBs). Carbon materials with variant structures have shown great effect of Li protection in liquid electrolytes, however, can accelerate the solid‐state electrolyte (SE) decomposition owing to the high electronic conductivity, seriously limiting their application in ASSLMBs. Here, a novel strategy is proposed to tailor the carbon materials for efficient Li protection in ASSLMBs, by in situ forming a rational niobium‐based Li‐rich disordered rock salt (DRS) shell on the carbon materials, providing a favorable percolating Li⁺ diffusion network for speeding the carbon lithiation, and enabling simultaneously improved lithiophilicity and reduced electronic conductivity of the carbon structure at deep lithiation state. Using the proposed strategy, different carbon materials, such as graphitic carbon paper and carbon nanotubes, are tailored with great ability to speed the interfacial kinetics, homogenize the Li plating/stripping processes, and suppress the SE decompositions, enabling much improved performances of ASSLMBs under various conditions approaching the practical application. This strategy is expected to create a novel roadmap of Li protection for developing reliable high‐energy‐density ASSLMBs.