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Using stable inorganic solid electrolyte to replace organic liquid electrolyte could significantly reduce potential safety risks of rechargeable batteries. Na-superionic conduc-tor (NASICON)-structured solid electrolyte is one of the most promising sodium solid electrolytes and can be employed in solid-state sodium batteries. In this work, a NASICON-structured solid electrolyte Na3.1Zr1.95Mg0.05Si2PO12 was synthesized through a facile solid-state reaction, yielding high sodium-ionic conductivity of 1.33 × 10-3 S·cm-1 at room temperature. The results indicate that Mg2+is a suitable and economical substitution ion to replace Zr4+, and this synthesis route can be scaled up for powder preparation with low cost. In addition to electrolyte material preparation, solid-state bat-teries with Na3.1Zr1.95Mg0.05Si2PO12 as electrolyte were assembled. A specific capacity of 57.9 mAh·g-1 is main-tained after 100 cycles under a current density of 0.5C rate at room temperature. The favorable cycling performance of the solid-state battery suggests that Na3.1Zr1.95Mg0.05Si2PO12 is an ideal electrolyte candidate for solid-state sodium batteries.