Herein we report the design and synthesis of fluorine-doped, carbon-encapsulated hollow Fe3O4 spheres (h-Fe3O4@C/F) through mild heating of polyvinylidene fluoride (PVDF)-coated hollow Fe3O4 spheres. The spheres exhibit enhanced cyclic and rate performances. The as-prepared h-Fe3O4@C/F shows significantly improved electrochemical performance, with high reversible capacities of over 930 mA h g(-1) at a rate of 0.1 C after 70 cycles, 800 mA h g(-1) at a rate of 0.5 C after 120 cycles and 620 mA h g(-1) at a rate of 1 C after 200 cycles. This improved lithium storage performance is mainly ascribed to the encapsulation of the spheres with fluorine-doped carbon, which not only improves the reaction kinetics and stability of the solid electrolyte interface film but also prevents aggregation and drastic volume change of the Fe3O4 particles. These spheres thus represent a promising anode material in lithium-ion battery applications.