The electrochemical performance of a novel all solid-state sodium-ion symmetrical battery with Na3Zr2Si2PO12 (NASICON) as a solid electrolyte and Na3V2(PO4)3 (NVP) as the active electrode material was examined. The all solid-state cell was fabricated by a combination of screen printing and hot pressing. The electrochemical characterization of the NVP active material in the metallic sodium half-cells at 80°C indicated that this NASICON-related phosphate undergoes reversible sodium extraction/insertion reactions at electrode potentials of 1.6 and 3.4V vs. Na. These insertion properties allowed the NVP to function successfully as the active material for both the positive and negative electrodes in a sodium-ion cell configuration. A charge–discharge cycling test of the fabricated symmetrical all solid-state cell was carried out at room temperature within the voltage range of 0.01 and 1.9V. It was found that the cell can work as a secondary battery and showed first discharge capacities of 68 and 32mAhg−1 at the current densities of 1.2 and 10μAcm−2, respectively. Furthermore, the lack of reactivity between the all-solid-state cell components during long-term cycling was confirmed.