Lithium metal batteries have garnered significant attention as promising energy storage solutions. However, their performance is often compromised by the risks associated with highly active metallic lithium, unrestricted electrode expansion, and excessive dendrites growth. Here we introduce an advanced lithiophilic anode substrate designed by chemically patterning technology for multiple security enhancements. The innovative lithiophilic array harmonizes spatial Li+ to prepare compact and reversible electrodes. The composite electrodes feature an enhanced C–F component in the solid‐electrolyte interface, which protects the deposited lithium metal from unwanted side reactions, thereby stabilizing electrochemical cycling. Notably, the thermal safety can be revealed through the substrate's excellent catalytic ability to convert smoke and toxic gases during extreme thermal runaway. This work demonstrates a novel approach to integrating battery cycling stability with thermal safety, paving the way for more reliable and secure energy storage systems.