The feasibility of sodium-ion batteries as an alternative to lithium-ion batteries in large-scale storage systems largely depends on the availability of advanced electrode materials leading to enhanced energy density and operational sustainability. Herein, we present a novel β-polymorph of sodium vanadium pyrophosphate NaVP2O7 with the KAlP2O7-type structure obtained via hydrothermal synthesis and further thermal dehydration of a hydrophosphate intermediate. β-NaVP2O7 demonstrates attractive electrochemical behavior as a Na-ion positive electrode (cathode) material with practically achieved a reversible capacity of 104 mAh/g at C/10 current density, an average operating voltage of 3.9 V vs Na/Na+, and only 0.5% volume change between the charged and the discharged states. Electrode material exhibits excellent C-rate capability and cycling stability, providing a capacity of 90 mAh/g at 20C discharge rate and <1% capacity loss after 100 charge-discharge cycles. In the low-voltage region (≈1.5 V vs Na/Na+), β-NaVP2O7 reversibly intercalates additional sodium cations, leading to extraordinary overall Na-ion storage ability exceeding 200 mAh/g within the 1.5-4.4 V vs Na/Na+ voltage region. This material is one of only a few materials that exhibit reversible sodium-ion storage over such a large potential window.