The multi-wall carbon nanotubes wired spherical Fe2F5·H2O particles (MWCNTs-wired Fe2F5·H2O) are synthesized via an ionic liquid (IL) based precipitation route as the cathode material for sodium ion batteries (SIBs), in which the IL 1-butyl-2,3-dimethylimidazolium tetrafluoroborate (BMMimBF4) is used as environmentally friendly fluorine source, appropriate solvent and binder. The structure, morphology and electrochemical performance of the as-prepared samples have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), charge/discharge tests, cyclic voltammetric measurements (CV). The results show that the MWCNTs-wired spherical Fe2F5·H2O particles present the cubic crystal structure with the cell volume of 1.12821 nm3. Moreover, the SEM and TEM images show that the spherical Fe2F5·H2O particles and disentangled MWCNTs are intertwined together to form a chestnut-like micrometer-sized aggregates. Furthermore, the MWCNTs-wired spherical Fe2F5·H2O particles show a high initial discharge capacity of 251.2 mAh g−1 at 20 mA g−1 in the voltage of 1.0–4.0 V, and the corresponding reversible discharge capacity is 197.4 mAh g−1. Comparing with bare Fe2F5·H2O, the discharge capacity of the MWCNTs-wired spherical Fe2F5·H2O particles still can maintain about 115.0 mAh g−1 after 50 cycles when the current density increased to 100 mA g−1, and the corresponding capacity retention reaches 90.2%.