We have entered the age of renewable energy revolution. Hence, energy-dense all-solid-state lithium metal batteries are now being actively researched as one of the most promising energy storage systems. However, they have not yet been a silver bullet due to the dendrite formation and interfacial issue. Here, we introduce the hybrid polymer electrolyte via a novel solvent-free strategy as well as utilize a polymerization and gelation effect of cyanoethyl polyvinyl alcohol to achieve superior electrochemical performance. The hybrid polymer electrolyte, using cyanoethyl polyvinyl alcohol, demonstrates a stable artificial solid electrolyte interface layer, which suppresses the continuous decomposition of Li salts. Importantly, we also present the lithium-graphite composite anode to reach the super-high-energy-density anode materials. Taken together, these advancements represent a significant stride toward addressing the challenges associated with all-solid-state lithium metal batteries.