© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Iron sulfides with high theoretical capacity and low cost have attracted extensive attention as anode materials for sodium ion batteries. However, the inferior electrical conductivity and devastating volume change and interface instability have largely hindered their practical electrochemical properties. Here, ultrathin amorphous TiO2 layer is constructed on the surface of a metal–organic framework derived porous Fe7S8/C electrode via a facile atomic layer deposition strategy. By virtue of the porous structure and enhanced conductivity of the Fe7S8/C, the electroactive TiO2 layer is expected to effectively improve the electrode interface stability and structure integrity of the electrode. As a result, the TiO2-modified Fe7S8/C anode exhibits significant performance improvement for sodium-ion batteries. The optimal TiO2-modified Fe7S8/C electrode delivers reversible capacity of 423.3 mA h g−1 after 200 cycles with high capacity retention of 75.3% at 0.2 C. Meanwhile, the TiO2 coating is conducive to construct favorable solid electrolyte interphase, leading to much enhanced initial Coulombic efficiency from 66.9% to 72.3%. The remarkable improvement suggests that the interphase modification holds great promise for high-performance metal sulfide-based anode materials for sodium-ion batteries.