Recently, sodium has reattracted scientists' interest in using in rechargeable battery for its low cost and abundant amount compared with lithium. All-solid-state sodium metal battery is doomed to have promising future for its theoretically high capacity (1166mAh/g), non-flammability and low cost. Here, we fabricated a polyethylene oxide (PEO) based hybrid solid electrolyte which showed low glass transition temperature, absence of crystallization and ionic conductivity greater than 1×10-4 S/cm at 80 °C. The solid electrolyte showed low interface resistance (~100ohms at 80C) with sodium metal and high stability in cycling test, with Cd reaching 3000C/cm2 at current density 0.5mA/cm2. All-solid-state sodium metal battery using thermal-treated vanadium oxide as active material, the hybrid polymer as the electrolyte and separator, and pristine sodium metal as the anode. The battery showed excellent capacity (300mAh/g) and good coulombic efficiency. Detailed sodium dendrite growth and electrolyte depletion in have also been systematically studied. Our work showed that the hybrid network is promising for all-solid-state sodium battery applications.