Transition metal oxides have been considered as the next lithium-ion batteries (LIBs) anode materials because of their ultrahigh specific capacity, tunable redox reaction, high stability, and low cost. However, their shortcomings of inherent large volume expansion (except titanium dioxide and vanadium pentoxide), low conductivity, and poor reaction kinetics seriously hinder the practical applications in LIBs. To overcome these problems, non-hierarchical heterostructure FeO/FeF porous spheres (NHFs) are designed and successfully prepared by the simultaneously adsorption of fluoride ions during the formation of the precursor with a facile one-pot self-assembly approach. Compared with traditional counterparts, the NHF exhibits high structural stability and improved reaction dynamics upon repeated electrochemical lithiation/delithiation. Furthermore, NHF exhibits an outstanding reversible capacity of 765 mA h g at the current density of 0.2 A g, an excellent rate capability of 265 mA h g at 10 A g, and an eminent cyclability with a capacity retention of 87.4% after 3000 cycles.