Non-aqueous sodium-ion batteries (SiBs) are a viable electrochemical energy storage system for grid storage. However, the practical development of SiBs is hindered mainly by the sluggish kinetics and interfacial instability of positive-electrode active materials, such as polyanion-type iron-based sulfates, at high voltage. Here, to circumvent these issues, we proposed the multiscale interface engineering of Na Fe (SO ) , where bulk heterostructure and exposed crystal plane were tuned to improve the Na-ion storage performance. Physicochemical characterizations and theoretical calculations suggested that the heterostructure of Na Fe(SO ) phase facilitated ionic kinetics by densifying Na-ion migration channels and lowering energy barriers. The (11-2) plane of Na Fe (SO ) promoted the adsorption of the electrolyte solution ClO anions and fluoroethylene carbonate molecules, which formed an inorganic-rich Na-ion conductive interphase at the positive electrode. When tested in combination with a presodiated FeS/carbon-based negative electrode in laboratory- scale single-layer pouch cell configuration, the Na Fe (SO ) -based positive electrode enables an initial discharge capacity of about 83.9 mAh g , an average cell discharge voltage of 2.35 V and a specific capacity retention of around 97% after 40 cycles at 24 mA g and 25 °C.