Lithium metal batteries (LMBs) are among the most promising candidates for high energy-density batteries. However, dendrite growth constitutes the biggest stumbling block to its development. Herein, Li4SiO4-dominating organic-inorganic hybrid layers are rationally designed by SiO2 surface modification and the stepwise prelithiation process. SiO2 nanoparticles construct a zigzagged porous structure, where a solid electrolyte interface (SEI) has grown and penetrated to form a conformal and compact hybrid surface. Such a first-of-this-kind structure enables enhanced Li dendrite prohibition and surface stability. The interfacial chemistry reveals a two-step prelithiation process that transfers SiO2 into well-defined Li4SiO4, the components of which exhibits the lowest diffusion barrier (0.12 eV atom-1) among other highlighted SEI species, such as LiF (0.175 eV atom-1) for the current artificial layer. Therefore, the decorated Li allows for an improved high-rate full-cell performance (LiFePO4/modified Li) with a much higher capacity of 65.7 mAh g-1 at 5C (1C = 170 mAh g-1) than its counterpart with bare Li (∼3 mAh g-1). Such a protocol provides insights into the surface architecture and SEI component optimization through prelithiation in the target of stable, dendrite-proof, homogenized Li+ solid-state migration and high electrochemical performance for LMBs.