Here we report a polyanion-based cathode material for sodium-ion batteries, Na2MnSiO4, registering impressive sodium storage performances with discharge capacity of 210 mAh g−1 at an average voltage of 3 V at 0.1 C, along with excellent long-term cycling stability (500 cycles at 1 C). Insertion/extraction of ∼1.5 mol of sodium ion per formula unit of the silicate-based compound is reported and the utilisation of Mn2+ ⇋ Mn4+ redox couple is also demonstrated by ex-situ XPS. Besides, this study involves a systematic investigation of influence of the electrolyte additive (with different content) on the sodium storage performance of Na2MnSiO4. The electrolyte additive forms an optimum protective passivation film on the electrode surface, successfully reducing manganese dissolution.