AbstractThe propensity of lithium dendrite formation during the charging process of lithium metal batteries is linked to inhomogeneity on the lithium surface layer. The high reactivity of lithium and the complex surface structure of the native layer create “hot spots” for fast dendritic growth. Here, it is demonstrated that a fundamental restructuring of the lithium surface in the form of lithium silicide (LixSi) can effectively eliminate the surface inhomogeneity on the lithium surface. In situ optical microscopic study is carried out to monitor the electrochemical deposition of lithium on the LixSi‐modified lithium electrodes and the bare lithium electrode. It is observed that a much more uniform lithium dissolution/deposition on the LixSi‐modified lithium anode can be achieved as compared to the bare lithium electrode. Full cells paring the modified lithium anode with sulfur and LiFePO4 cathodes show excellent electrochemical performances in terms of rate capability and cycle stability. Compatibility of the anode enrichment method with mass production process also offers a practical way for enabling lithium metal anode for next‐generation lithium batteries.