Rechargeable lithium ion batteries have ruled the consumer electronics market for the past 20 years and have great significance in the growing number of electric vehicles and stationary energy storage applications. However, in addition to concerns about electrochemical performance, the limited availability of lithium is gradually becoming an important issue for further continued use and development of lithium ion batteries. Therefore, a significant shift in attention has been taking place towards new types of rechargeable batteries such as sodium-based systems that have low cost. Another important aspect of sodium battery is its potential compatibility with the all-solid-state design where solid electrolyte is used to replace liquid one, leading to simple battery design, long life span, and excellent safety. The key to the success of all-solid-state battery design is the challenge of finding solid electrolytes possessing acceptable high ionic conductivities at room temperature. Herein, we report a novel sodium superionic conductor with NASICON structure, Na3.1Zr1.95Mg0.05Si2PO12 that shows high room-temperature ionic conductivity of 3.5 × 10-3S cm-1. We also report successful fabrication of a room-temperature solid-state Na-S cell using this conductor.