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Nanoscale Fe3O4-Sn@CNFs was prepared by loading Fe3O4 and Sn nanoparticles onto CNFs synthesized via electrostatic spinning and subsequent thermal treatment by solvothermal reaction, and were used as anode materials for lithium-ion batteries. The prepared anode delivers an excellent reversible specific capacity of 1120 mAh·g−1 at a current density of 100 mA·g−1 at the 50th cycle. The recovery rate of the specific capacity (99%) proves the better cycle stability. Fe3O4 nanoparticles are uniformly dispersed on the surface of nanofibers with high density, effectively increasing the electrochemical reaction sites, and improving the electrochemical performance of the active material. The rate and cycling performance of the fabricated electrodes were significantly improved because of Sn and Fe3O4 loading on CNFs with high electrical conductivity and elasticity.