Developing high-performing solid electrolytes that could replace flammable organic liquid electrolytes is vital in designing safer solid-state batteries. Among the sodium-ion (Na + ) conducting solid electrolytes, Na-β″-alumina (BASE) is highly regarded for its employment in solid-state battery applications due to its high ionic conductivity and electrochemical stability. BASE has long been employed in commercial Na−NiCl 2 and Na−S batteries. However, the synthesis of highly conductive BASE is energy-intensive, involving elevated temperatures for sintering and the incorporation of stabilizing additives. Additionally, BASE is highly sensitive to humidity, which limits its applications. Hence, there is an intense search to identify suitable high-performing solid electrolytes that could replace BASE. In this context, we reinvestigated Na 5 GdSi 4 O 12 (NGS) and demonstrated that phase pure NGS could be synthesized by a simple solid-state reaction. Beyond a high ionic conductivity of 1.9 × 10 −3 S cm −1 at 30 °C (1.5 × 10 −3 S cm −1 for BASE), NGS exhibited high chemical as well as electrochemical stability, lower interfacial resistance, lower deposition and stripping potential, and higher short-circuiting current, designating NGS as a better solid electrolyte than BASE.