Innovative rechargeable batteries that can effectively store renewable energy, such as solar and wind power, urgently need to be developed to reduce greenhouse gas emissions. All-solid-state batteries with inorganic solid electrolytes and electrodes are promising power sources for a wide range of applications because of their safety, long-cycle lives and versatile geometries. Rechargeable sodium batteries are more suitable than lithium-ion batteries, because they use abundant and ubiquitous sodium sources. solid electrolytes are critical for realizing allsolid-state sodium batteries. Here we show that stabilization of a high-temperature phase by crystallization from the glassy state dramatically enhances the na + ion conductivity. An ambient temperature conductivity of over 10 − 4 s cm − 1 was obtained in a glass-ceramic electrolyte, in which a cubic na 3 Ps 4 crystal with superionic conductivity was first realized. All-solid-state sodium batteries, with a powder-compressed na 3 Ps 4 electrolyte, functioned as a rechargeable battery at room temperature.