Vital need to reduce battery cost inspired intensive research in the field of sodium-storage systems, which required extending the range of perspective electrode materials. Herein, we present a new member of the electrochemically active NASICON material family, rhombohedral NaMo2(PO4)3, which demonstrates both Mo+4/Mo+5 and Mo+4/Mo+3 redox activities towards sodium (de)intercalation. Desodiation of the initial NaMo2(PO4)3 material with subsequent discharge within the 1.2–4.0 V range leads to a multi-electron redox transition with reversible capacity of 130 mAh g−1. However, the single Mo+4/Mo+3 redox transition at 2.45 V (vs. Na/Na+) with capacity of 95 mAh g−1 was found to be more stable during cycling, and operando X-ray diffraction confirmed its two-phase mechanism. Sodiation of the initial phase results in Na2.5Mo2(PO4)3, which maintains the parent NASICON structure (R-3c, a = 8.90532(7) Å, c = 22.2379(3) Å, V = 1527.30(3) Å3), with two Na-positions being almost equal in occupancy and energy.