The ability to implement a lithium metal anode is regarded as enabling technology for next-generation high-energy-density rechargeable batteries. However the unstable interface between the metallic lithium and electrolytes leads to formation of lithium dendrite that can result in both low Coulombic efficiencies and ultimately cell failure. In this work, we explore the promise of implementing a “purpose made” SEI layer directly onto the metallic lithium surface to counter deleterious effects. Specifically, polymer/inorganic composites containing hybrid nanoparticles were prepared by covalently grafting polyacrylontrile (PAN) from oxygen vacancy (Vo) rich yttria stabilized zirconia (YSZ) nanoparticles using atom transfer radical polymerization (ATRP). A thin layer of the YSZ-PAN hybrids was coated onto the surface of metallic lithium anode as an artificial SEI. It was found that the YSZ-PAN hybrids materials showed high ionic conductivity (> 10^-4S/cm at r.t.), improved transference number (>0.5) and robust mechanical strength. Due to these unique properties, the YSZ-PAN hybrids SEI greatly improved the lithium stripping/plating process with up to 600 hundred hours of symmetric cycling at 1 mA/cm² without voltage polarization.