Fe3O4@CNF anode material for Li-ion batteries (LIBs) was designed and fabricated using lyotropic cellulose acetate as the carbon nanofiber (CNF) phase and Fe(acac)3 as the Fe3O4 phase through the electrospinning approach. Because the CNFs could retard the change of Fe3O4 volume during the electrochemical cycling and improve the electrical conductivity and the introduction of Fe3O4 could offer a larger specific surface area and more mesopores to promote electrolyte penetration and Li+ diffusion, the Fe3O4@CNFs electrode showed high reversible capacities (RCs) of 773.6 and 596.5 mAh g-1 after 300 cycles and capacity residuals of 98.0 and 99.0% at high current densities 1 and 2 A g-1, respectively. This simple method to fabricate Fe3O4@CNFs composite as anode material can be widely applied to fabricate metal oxides and bio-carbon composite nanofibers for high-performance energy storage materials.