The role of iron in Na 1.5Fe 0.5Ti 1.5(PO 4)3/C electrode material for Na batteries has been studied by 57Fe Mössbauer spectroscopy in operando mode. The potential profile obtained in the galvanostatic regime shows three plateaus at different voltages due to different reaction mechanisms. Two of them, at 2.2 and 0.3 V vs Na +/Na 0, have been associated to redox processes involving iron and titanium in Na 1.5Fe 0.5Ti 1.5(PO 4)3. The role of titanium was previously elucidated for NaTi 2(PO 4)3 and the effect of the substitution of Fe for Ti was investigated with 57Fe Mössbauer spectroscopy. We show that iron is an electrochemically active center at 2.2 V with the reversible Fe 3+/Fe 2+ transformation and then remains at the oxidation state Fe 2+ along the sodiation until the end of discharge at 0 V.